CN1689962A - Method for producing synthetic gas by gasifying super-heavy inferior oil mixture - Google Patents
Method for producing synthetic gas by gasifying super-heavy inferior oil mixture Download PDFInfo
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- CN1689962A CN1689962A CN 200410018120 CN200410018120A CN1689962A CN 1689962 A CN1689962 A CN 1689962A CN 200410018120 CN200410018120 CN 200410018120 CN 200410018120 A CN200410018120 A CN 200410018120A CN 1689962 A CN1689962 A CN 1689962A
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- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000000203 mixture Substances 0.000 title claims description 17
- 239000007789 gas Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 60
- 239000010426 asphalt Substances 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 44
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 230000036961 partial effect Effects 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 147
- 238000002156 mixing Methods 0.000 claims description 58
- 239000006229 carbon black Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 25
- 238000002309 gasification Methods 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 238000004523 catalytic cracking Methods 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000007701 flash-distillation Methods 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- 239000010797 grey water Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000000194 supercritical-fluid extraction Methods 0.000 claims description 3
- 231100000331 toxic Toxicity 0.000 claims description 3
- 230000002588 toxic effect Effects 0.000 claims description 3
- 238000003973 irrigation Methods 0.000 claims description 2
- 230000002262 irrigation Effects 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004202 carbamide Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 description 19
- 239000002994 raw material Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 14
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- 239000000126 substance Substances 0.000 description 10
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- 239000003054 catalyst Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000004227 thermal cracking Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 206010062717 Increased upper airway secretion Diseases 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 208000026435 phlegm Diseases 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- APTZNLHMIGJTEW-UHFFFAOYSA-N pyraflufen-ethyl Chemical compound C1=C(Cl)C(OCC(=O)OCC)=CC(C=2C(=C(OC(F)F)N(C)N=2)Cl)=C1F APTZNLHMIGJTEW-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The process of gasifying super heavy inferior mixed oil to produce synthetic gas is to feed oxygen-containing gas, oil slurry and optional moderator into the oxidation area for partial oxidation. The present invention features that the mixed oil as material comprising at least deoiled asphalt from oil refinery in 60-95 wt% and oil slurry in 5-30 wt%. The mixed oil is made to enter to the gasifying area of the multiple nozzle gasifying furnace through the nozzles with entrance temperature of 240-280 deg.c and oxidized partially at 1400-1450 deg.c. The present invention can utilize various kinds of oil residue and oil slurry from oil refinery comprehensively to produce synthetic gas for producing urea.
Description
Technical field
The present invention relates to a kind of hydrocarbon containing fuels and carry out the technical field of portion oxidation synthesis gas.
Background technology
From the nineties later stage,, be that the economic benefit of the chemical fertilizer plant of raw material progressively descends with residual oil along with the rise of fuel oil price.Particularly after the second half year in 2000, international and domestic residual oil price is soaring significantly, the urea product price then is decline situation, the ammonia-preparing device that with residual oil is raw material can't bear the raw materials cost elevated pressure, domestic device of the same type is all hard to carry on, and a lot of companies chemical fertilizer plant loss occurred after 2000.For reversing the unfavorable situation of chemical fertilizer plant as early as possible, scientific and technical personnel are actively seeking the prioritization scheme that chemical fertilizer is detracted, made up deficits always.Certainly also the someone expects that coal with relative low price gasifies and comes gas making to produce urea, and is very huge but its drawback of bringing is facility investment, makes the people in a dilemma.So people expect very naturally, the de-oiled asphalt that will contain higher bituminous matter and carbon residue under certain gasification condition, mixes a certain amount of oxygen-containing gas, make hydrocarbon partial oxidation become synthetic gas to produce chemical fertilizer, thereby realized reducing the purpose of synthetic gas production cost.
External super major company carries out partial oxidation system gas to residual hydrocarbon through the de-oiled asphalt that obtains behind the solvent deasphalting treatment process very deep research, as the patent No. is that the Chinese patent of 94104601.X " is used for hydrocarbon containing fuels is carried out the method for partial oxidation ", this kind is used for hydrocarbon containing fuels is carried out the method for partial oxidation, it may further comprise the steps: under suitable reaction conditions, with oxygen-containing gas, hydrocarbon containing fuels and randomly moderator gas infeed the gasification zone, use wherein acts as a fuel the heavy still bottoms raw material, it is characterized in that, the heavy still bottoms raw material is a Cn-pitch, wherein n is 4 or bigger, under suitable condition this Cn-pitch is infeeded the gasification zone by at least one multi-nozzle (ring-type altogether) burner.This method has realized the poor qualityization of gasified raw material, this is its progressive one side, but its defective is that de-oiled asphalt viscosity is too high, when going vapourizing furnace to carry out partial oxidation gas making, reach good atomizing effect, this de-oiled asphalt must be preheating to very high temperature, generally more than 280 ℃, cause de-oiled asphalt in pipeline and the coking fouling of nozzle place thus easily, can't satisfy the long-term operation requirement, in case and preheating temperature when not high enough, then atomizing effect is poor, cause the gas volume of effective synthetic gas few, efficiency of conversion descends, and treatment capacity also descends, the heavy still bottoms utilization ratio is low, in addition the Cn-asphalt component is removed partial oxidation, also have a unsafe factor here, because this Cn-asphalt component contains a large amount of solvents, though passed through the pitch stripping tower, but still contain several percentage points quantity of solvent in the Cn-asphalt component, head tank causes the industrial production accident easily, so also require further improvement.The patent No. is that 951027166 Chinese patent " transforms the method for residual hydrocarbon ils ", to obtain after the residual hydrocarbon ils diasphaltene: the gross weight with the residual hydrocarbon ils of heavy is a benchmark, deasphalted oil (DAO) productive rate is at least 50% (by weight), with part or all of DAO by the thermally splitting district, like this, vaporization temperature is a benchmark in the raw material gross weight more than 520 ℃ in the thermally splitting raw material, makes this part conversion of raw material be at least 60% (by weight).This patent document has also further been mentioned and has been utilized the cracking-residuum that finally obtains after the cracking and handle resulting bituminous matter component from diasphaltene and mix, and the mixed solution of gained is gasified come gas making then.Though this processing method has improved the transformation efficiency of thermally splitting, obtain the cut of better quality, with mass ratio better, the fewer deasphalted oil of the bituminous matter component concentration cracking technology of reducing phlegm and internal heat still has the leeway of discussion.First, the deasphalted oil cracking treatment process that reduces phlegm and internal heat produces some lighting ends such as products such as diesel oil, gasoline, need the newly-increased thermal cracker of a cover, and the fair lighting end quality of going hydrogenation, catalytic cracking process to produce than deasphalted oil of the lighting end that produces of this technology is poor; Secondly, the higher de-oiled asphalt of bituminous ratio of component be with thermally splitting after residual oil mix again, obtaining mixed solution goes to gasify, there are some related problems of a top patent equally, defective such as bad as atomizing effect, that transformation efficiency is low, aerogenesis is few influences the effect of these some material partial oxidations.
In addition, the oil refining production equipment also produces such as by products such as catalytically cracked oils, so-called catalytic cracking unit slurry oil is meant oil at the bottom of stock oil is through the tower that forms behind the catalytic cracking reaction and be present in the catalytic cracking fractionating tower bottom, it generally contains catalytic cracking catalyst 1000-10000ppm, it is generally aluminum oxide and silicon oxide is carrier, its stable hydrocarbon accounts for 50-60 (wt) %, and aromatic hydrocarbons accounts for 35-45 (wt) %, and colloid and bituminous matter respectively account for 1-5 (wt) %.Owing to contain a large amount of condensed-nuclei aromaticss, its viscosity is very low, good flowing properties.But, make its utility value descend greatly owing to contain catalytic cracking catalyst in the catalytic slurry.If adopt and to mix a certain proportion of catalytically cracked oil in the full-bodied de-oiled asphalt and make gasified raw material production of synthetic gas in next life, then can reduce the viscosity of mixing raw material greatly, advance the preceding preheating temperature of nozzle thereby reduce mixing oil.Therefore utilize these slurry oils as gasified raw material, the necessity of making use of momentum is considered the influence of catalyst powder foot couple gasifier operation.So, realize utilizing de-oiled asphalt and catalytically cracked oil, need a kind of new partial oxidation technology method of exploitation, de-oiled asphalt and catalytically cracked oil are fully utilized, simultaneously, solve the influence of the catalyst powder foot couple gasifier operation of bringing in the raw material residual oil.
Summary of the invention
Technical problem to be solved by this invention is the method that provides a kind of overweight mixing oil gasification inferior to produce synthetic gas at existing background technology, it can carry out partial oxidation gas making to the multiple dregs of fat or the slurry oil that exists in the refinery production, use for producing urea, improve the business economic benefit, and the miscella preheating temperature is low, atomizing effect is good in vapourizing furnace, factor of created gase is high.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the method that synthetic gas is produced in a kind of overweight mixing oil gasification inferior, it is with oxygen-containing gas, slurry oil and optional moderator gas infeed the gasification zone, carry out partial oxidation, it is characterized in that described partial oxidation raw material adopts de-oiled asphalt and slurry oil to mix, mixing oil comprises de-oiled asphalt 60-95 (wt) % that processing produces through solvent deasphalting unit and slurry oil (Residual oil) 5-30 (wt) % that processing produces through catalytic cracking unit at least, be under 240-280 ℃ the conditions suitable in the gasifying furnace nozzle temperature in, mixing oil is entered the gasification zone by the multi-nozzle vapourizing furnace, in 1400-1450 ℃ of scope, carry out partial oxidation.
Useful is, above-mentioned gasifying furnace nozzle temperature in is 260-265 ℃, and the mixing oil viscosity in this moment most of ratio ranges is at the 20-40 centipoise, flowability and atomization are relatively good, Jia Re temperature is also proper simultaneously, implements easily, reduces heating cost.
Useful is, above-mentioned de-oiled asphalt is that mixed residue oil obtains Cn-pitch from the solvent deasphalting technological process, n is 3,4,5 or bigger, deasphalting processing method those skilled in the art know, typically refer to residual oil and solvent from residual oil, to remove oil ingredient, thereby the acquisition de-oiled asphalt is gone into partial oxidation gasification production synthetic gas as having very full-bodied overweight raw material.
What be highly profitable is, above-mentioned solvent deasphalting technological process is to adopt C4-supercritical extraction isolation technique, solvent adopt propane, butane, pentane (comprise they just, isomer), and their mixture, and in conjunction with supercritical extraction technology production deasphalted oil, by-product de-oiled asphalt.
Useful is, its extraction degree of depth of above-mentioned solvent deasphalting technological process is 45-75 (wt) %, with the residual hydrocarbon total amount that enters the solvent deasphalting technological process is benchmark, make the solvent deasphalting technological process can obtain many deasphalted oil DAO like this, simultaneously can avoid again producing too heavy-gravity pitch, make de-oiled asphalt can be fit to the partial oxidation gasification of next step.
Above-mentioned this residual hydrocarbon is the residual oil that produces from the oil refining vacuum distillation apparatus, and above-mentioned slurry oil is for comprising wax oil, the stock oil of long residuum and/or mixtures of residua is through Residual oil that form and that be present in the catalysed fractionation tower bottom behind the catalytic cracking reaction, it generally contains catalytic cracking catalyst 1000-10000PPM, stable hydrocarbon accounts for 50-60 (wt) %, aromatic hydrocarbons accounts for 35-45 (wt) %, colloid and bituminous matter respectively account for 1-5 (wt) %, 50 ℃ viscosity is about 200 centipoises, certain blend component as mixing oil, also can adopt the Residual oil of other device by-product of oil refining, as thermal cracking residue, normal decompression washing oil or the like makes the partial oxidation gasifying process can make full use of difficult these Residual oils by other approach digestion of oil refining.
Useful is, above-mentioned mixing oil in the viscosity controller of vapourizing furnace ingress in 20-40 centipoise scope, make mixing oil can keep good flowing property, effect such as reach that atomizing effect is good, gasification turnover ratio height, gas production rate are big, if the feeding preheating device had been installed before vapourizing furnace, and that mixing oil is brought up to is the highest 280 ℃, make mixing oil can keep good flowing property, be not easy on pipeline, to lump, blocking pipe or influence its atomizing effect on the nozzle of vapourizing furnace.
What be highly profitable is, above-mentioned Cn-pitch is mixed into mixing oil with oil at the bottom of the tower with solvent extraction through air-lift device again after the PPM rank is several PPM, in common solvent diasphaltene technological process, the Cn-asphalt component is removed solvent through air-lift device, can only drop to several percentage points degree, bring some unsafe factors can for like this actual production technology, oil refining apparatus is in some time, need to handle emergency episode or adjust production status, mixing oil need be filled in the intermediary storage tank and store, so the solvent in the mixing oil is too high, cause easily and in storage tank, parse too much inflammable gas (being exactly the gas form of solvent), run into static or thunderbolt, cause explosion hazard.
Very perfect design is, its carbon black water that comes out of above-mentioned vapourizing furnace is earlier through an interchanger, the preferential employing of described interchanger vertical tubular heat exchange capable of washing, carry out heat exchange with the buck that returns the use of carbon black washing tower, reduce to 140～180 ℃, grey water temp then is increased to 180～210 ℃, reclaims high level heat, earlier directly carry out the one-level flash distillation, to remove process gas CO, the H that is dissolved in the carbon black water
2And H
2S, guarantee in the postorder carbon black water no longer content toxic and harmful, further make simultaneously the carbon black water for cooling, afterwards, carry out follow-up extraction treatment and/or sedimentation filtration treatment again, it fully takes into account and utilizes mixing oil to carry out the detrimentally affect that high metal ash content that partial oxidation gas producing brings may cause vapourizing furnace, utilize carbon black open circuit technology, the ash content of the high metal content that mixing oil brought can be shifted out outside the gasifying furnace device in time, prolong operation cycle, can be stably, operation well, has less investment simultaneously, flow process is simple, reasonable energy utilization, also can realize using extraction process and sedimentation filtration method to handle the advantages such as flow process switching of carbon black water flexibly, particularly adopt vertical tubular heat exchange capable of washing to replace traditional U type tube heat-exchanger, solved the problem that the carbon black water-to-water heat exchanger stops up and can't clean easily.
What be highly profitable is, add wash-down water on the process gas pipeline of above-mentioned vapourizing furnace outlet and carry out spray irrigation, in carbon black washing tower exit strainer being set filters, the problem that it can effectively avoid too much carbon black that mixing oil brings and multiple metal ion to stop up vapourizing furnace process pipeline and strainer easily, and processing method is simple, implement easily, processing cost is cheap.
At last, its nozzle of above-mentioned vapourizing furnace is that the nozzle cooling tube is watered all-in-one-piece together with the fuel oil urceolus with high-density refractory casting material, and it has protected nozzle head to be subjected to the ablation of high-temperature gas well, and reduces burner cooling backwater temperature.
Compared with prior art, the invention has the advantages that: it utilizes residual oil that oil refining apparatus processing produces or waste oil as blend component, the de-oiled asphalt DOA that processing produces to solvent deasphalting unit is in harmonious proportion, some physicalies of single de-oiled asphalt have been improved, as reduce its viscosity, improve its flowability, make mixing oil atomizing effect in vapourizing furnace good, energy-conservation, the factor of created gase height, further reduce production costs, the residual oil that its physical properties and chemical composition are adopted near original vapourizing furnace as far as possible, making oil refining apparatus can make full use of original production facility fully utilizes the multiple dregs of fat or the slurry oil that exists in producing, be used for carrying out partial oxidation gas making, use for producing urea, improve the business economic benefit, and suitably improve the temperature of vapourizing furnace burner hearth, can prevent aluminium, metals such as silicon are piled up in the combustion chamber, prolong the cycle of operation of vapourizing furnace.
Description of drawings
Fig. 1 is overweight mixing oil combination process schematic flow sheet inferior;
Fig. 2 carbon black water treatment method feel flow draw of block;
Fig. 3 vapourizing furnace quenched water feedway process flow sheet.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Examples of implementation 1:
A kind of heavy-gravity Residual oil product (for example short distance Residual oil) that the oil refining reduced pressure distillation process of knowing at the process those skilled in the art comes out, this short distance Residual oil is fed in the solvent deasphalting unit goes, carry out solvent deasphalting technology, solvent can adopt butane, comprise the mixture of normal butane or Trimethylmethane or their any proportionings, also can adopt propane, pentane and C thereof
3, C
4, C
5Mixed solvent, in solvent, add other additive, improve the dissolving power of solvent, have good selectivity simultaneously, and then obtain good separating effect, and reduce running cost.In order to simplify flow process, reduce purposes such as investment, at first adopt at home and do not establish one section critical extracting of colloid sedimenting system and supercritical recovery technology, making the undissolvable Cn-asphalt component of solvent is that de-oiled asphalt DOA discharges from the bottom of device, and deasphalted oil DAO discharges from the top of device, carrying out the condition of solvent deasphalting technology knows in this specialty, in critical temperature and emergent pressure scope, operate, general optimum temperature range is 120-150 ℃, pressure is at 4-5MPa, the extraction degree of depth is 45-75 (wt) %, with the residual hydrocarbon total amount that enters the solvent deasphalting technological process is benchmark, make the de-oiled asphalt DAO yield and the quality of acquisition can satisfy the production needs preferably, the heavy-gravity de-oiled asphalt of Huo Deing is unlikely to too thickness simultaneously, also is fit to next step technological operation.Deasphalted oil DAO goes hydrogenation, catalytic cracking unit, thereby produces the cut that comprises light constituents such as gasoline, diesel oil, and this has been other Technology category, and embodiments of the invention is just no longer done new elaboration to this technology circuit.
The de-oiled asphalt DOA that obtains through solvent deasphalting unit, can not directly remove the vapourizing furnace partial oxidation, must advanced promoting the circulation of qi carry, the solvent that comprises in the Cn-asphalt component is removed as far as possible, can reclaim solvent, reduce the usage charges of solvent, simultaneously can improve production security, present embodiment adopts heating steam to carry out gas and carries, is several PPM with the solvent extraction in the de-oiled asphalt to the PPM rank, can be in the time of necessary in conjunction with chemical assistant such as defoamer, improve decreasing ratio and remove speed, there is an advantage to be like this, because oil refining apparatus sometimes needs to handle emergency episode, make its vapourizing furnace can not in time handle the de-oiled asphalt of coming from gas stripping column, have to the de-oiled asphalt of surplus or similarly go the Residual oil of partial oxidation gasification to be stored in the storage tank, if contain too much solvent in the de-oiled asphalt, parse easily, be detained in storage tank, in case meet static sparking or thunderbolt, cause an explosion accident easily, so with the solvent removal in the de-oiled asphalt to the PPM level, just can further improve the security of this respect, guarantee the refinery production that can successfully go into operation.
In conjunction with residual oil that produces in the oil refining apparatus course of processing such as vacuum residuum, normal decompression washing oil, thermal cracking residue and catalytically cracked oil are modulated de-oiled asphalt as blend component, be mixed into mixing oil, make its physicals such as viscosity, softening temperature, the residual oil that proportion etc. use near original vapourizing furnace as far as possible, in present embodiment, oil at the bottom of employing 70 (wt) % de-oiled asphalt and 30 (wt) % tower, oil is to comprise that the stock oil of wax oil and mixtures of residua is through residual oil that form and that be present in the catalysed fractionation tower bottom behind the catalytic cracking reaction at the bottom of the tower, owing to adopt the method for mixing oil, overcome original simple de-oiled asphalt that adopts and carried out the drawback that the partial oxidation gasification is brought, viscosity as de-oiled asphalt can reach more than 10 times of original use residual oil, adopted heating means to improve its flowability exactly, be heated to 320 ℃, arrive vapourizing furnace through pipe-line transportation, inlet at vapourizing furnace keeps more than 280 ℃, also be difficult to make de-oiled asphalt to obtain good atomizing through behind the nozzle of vapourizing furnace, so its transformation efficiency and gas production rate are all undesirable, remain further to be improved, and we have adopted synthetic mixing oil, the Residual oil and the de-oiled asphalt that utilize catalytic cracking unit to produce are in harmonious proportion, reduce the viscosity of de-oiled asphalt, improve its flowability, improved its atomizing effect.So after oil mixes at the bottom of 70% de-oiled asphalt and 30% tower, carry through steam heating and spiral pump, mixing oil is transported to vapourizing furnace removes partial oxidation, make the synthetic gas that contains carbon monoxide and hydrogen.Successfully carry in transport pipe in order to make mixing oil, we adopt high pressure steam that mixing oil is heated in primary heater unit, generally be heated to 280 ℃, the ingress that makes mixing oil enter into vapourizing furnace can keep more than 260 ℃, make mixing oil remain on the viscosity of 20-40 centipoise, be convenient to its atomizing gasification, certainly the temperature of mixing oil can be heated to higher scope, can further reduce its viscosity, improves its flowing property, but, so also can consume a large amount of heat energy, so in actual production process, this technical professional can be as required and own heating condition of refining oil, mixing oil is heated to a rational temperature more, in addition, under the general condition, also need to import oxygenant and moderator in vapourizing furnace, 1400-1450 ℃ of scope, carry out the partial oxidation gasification, make mixing oil oxidation gasification well, produce the gas that contains carbon monoxide and hydrogen, remove the chemical fertilizers production device, produce chemical fertilizer and use.
Though in using mixing oil, we make the rerum natura of mixing oil near original residual oil that adopts as much as possible, but owing to adopted slurry oil, mix factors such as going up granules of catalyst inevitably, sneaked into the high-load de-oiled asphalt of pitch simultaneously, so, make the body of heater and the gas cycle cooling plating drum of vapourizing furnace be mixed with a lot of carbon black particles and metal ion, if adopt original vapourizing furnace and gas cycle cooling plating drum, certainly will cause that the metal ash oontent sharply rises in the system of its sealing, influence the ordinary production operation of vapourizing furnace, so, can't satisfy the long-term operation requirement of vapourizing furnace.In addition; contain a certain amount of carbon black and multiple metal ion in the vapourizing furnace process gas; be more prone to cause this process gas pipeline encrustation thus; or the chilling ring wall hole of vapourizing furnace there is obstruction; regular meeting takes place to add the operating load that deficiency influences vapourizing furnace because of vapourizing furnace quenched water flow; when serious even cause vapourizing furnace to be forced to stop; thereby have influence on the long-term operation of whole device; usually terms of settlement is carried out mechanical cleaning to this process gas pipeline after can only regularly vapourizing furnace being stopped; but this way wastes time and energy, and the cleaning difficulty is very big.For preventing that vapourizing furnace chilling ring wall hole is by obstructions such as dirty sheets, traditional way is to add filtering net on the pipeline before and after the chilling water pump, can play the effect of filtering dirty sheet though do like this, but there is following shortcoming in it: 1, this position is a high pressure line, it is big to increase the strainer cost of investment, it is not convenient, dangerous to clean construction yet; 2, on the pipeline the dirty sheet of strainer to accumulate capacity little, cause new obstruction point easily, do not satisfy the requirement of vapourizing furnace long-term operation,, need transform its vapourizing furnace and circulating pipe system for this reason.In order to prevent that metals such as aluminium, silicon from piling up in the combustion chamber of vapourizing furnace, need suitably to improve the temperature of burner hearth in addition, can cause the nozzle of vapourizing furnace to be more prone to ablate like this, influence the operational cycle of vapourizing furnace, also need to do further improvement.
In embodiments of the invention, as seen from Figure 3, wherein the overstriking square frame is an inventive point of the present invention in the flow process of figure, the process gas outlet of vapourizing furnace is arrived the Venturi separator by pipe connection, be connected to the input mouth of pipe of buck washing water on the Venturi separator, the process gas of Venturi separator outlet simultaneously is by the process gas import of pipe connection to the carbon black washing tower, be connected to the input mouth of pipe of washing water simultaneously on the carbon black washing tower, carbon black washing tower top connects shift converter by pipeline, the following tower quenched water outlet of carbon black washing tower by pipeline and chilling water pump with the chilling ring of quenched water tieback to vapourizing furnace, the carbon black water out of vapourizing furnace connects the carbon black treatment unit by pipeline, this also is that traditional vapourizing furnace quenched water is supplied with processing method, crucial part of the present invention is to be brought to chilling ring place for preventing because of the dirty sheet in the carbon black washing tower behind the chilling water pump, the outlet of tower quenched water adds strainer under the carbon black washing tower, its advantage is: (1), this strainer is a normal pressure, cost of investment is low, (2), owing to be in tower, it is big that its dirty sheet accumulates capacity.On the specific design; for preventing to cause the mercury vapour erosion because of filter stoppage; consider the aperture of chilling ring simultaneously; this strainer adopts 8～12 apertures; can solve this two aspects problem well simultaneously; simultaneously on the process gas outlet conduit of vapourizing furnace, drive the water hole into; make the prosopyle connect the pipeline of wash-down water; make on the vapourizing furnace outlet process gas pipeline and add a feedwater flushing line; reasonable design is that to make the prosopyle be symmetrically arranged on the process gas outlet conduit of vapourizing furnace; wash-down water can be charged into from process gas pipeline zygomorphy; make the internal surface of process gas pipeline form the water membrane protection, thereby reduce carbon black and metal ion and the chance that the pipeline inwall contacts, the speed of slowing down this process gas pipeline encrustation; flow and speed about water spray; the chemical industry technician makes a choice according to the actual process situation of gasifying furnace device, and can suitably align, and makes it obtain best spray effect; certainly the prosopyle also can be that ring-type is equally distributed, with further raising developing result.
In addition, in embodiments of the invention, as seen from Figure 2, the carbon black water that comes out from vapourizing furnace is after direct heat exchange, be divided into the two-way of can arbitrary proportion selecting control, wherein one the road flow to settler and enter original extraction plant, another road enters the sedimentation filtration treatment device that increases newly after flowing to a flash tank, and the follow-up circulation that back gained buck is filtered in flashed vapour that comes out from this flash tank and sedimentation then utilizes original extraction plant equipment to finish.
In the present embodiment, first from the carbon black water that vapourizing furnace comes out through an interchanger, carry out heat exchange with the buck that returns the use of carbon black washing tower, reclaim high level heat, wherein, interchanger adopts vertical tubular heat exchange capable of washing to replace traditional U type tube heat-exchanger, solved the problem that the carbon black water-to-water heat exchanger stops up and can't clean easily, the temperature of the carbon black water that comes out from described vapourizing furnace can be 220～250 ℃, with can reduce to 140～180 ℃ after the buck heat exchange, grey water temp then can be increased to 180～210 ℃, aforementioned three's temperature is controlled at 250 ℃ respectively in this example, 160 ℃, 200 ℃, afterwards, carry out follow-up extraction treatment and/or sedimentation filtration treatment again.Because of extraction procedure except that before entering settler earlier through aforementioned direct heat exchange, identical with original process, therefore no longer described.Following emphasis is described the sedimentation filtration procedure:
Carbon black water after reclaiming high level heat directly carries out the one-level flash distillation earlier, to remove CO, the H that is dissolved in the carbon black water
2And H
2Process gas such as S, guarantee in the postorder carbon black water no longer content toxic and harmful, further make simultaneously the carbon black water for cooling, afterwards, the carbon black water that comes out from above-mentioned flash tank carries out heat exchange with the buck that overflows from settling tank again, make carbon black water further be cooled to 60～80 ℃, reclaim this part heat simultaneously, enter settling tank again and carry out sedimentation, after the sedimentation, gained buck retrieval system as required utilizes again, and gained carbon black slurry is then through obtaining carbon black filter cake by-product after the filter filtration treatment, filtered water then as required retrieval system utilize again or as discharge of wastewater.
Carry out heat exchange with the buck that returns the use of carbon black washing tower earlier because of the carbon black water that will go out vapourizing furnace in the present embodiment, well recycled high level heat on the one hand, make the grey water temp that returns vapourizing furnace can arrive 210 ℃, thereby improve the vapour/gas ratio that advances carbon monodixe conversion stove process gas greatly, improve the final interconversion rate of carbon monoxide; Reduce the temperature of carbon black water on the other hand, thereby can directly adopt the one-level flash distillation, and need not multistage flash evaporation, simplified technical process, facility investment is few; In addition, control loop is few, and regulating working conditions is steady, and is easy to operate; Also can switch flexibly and the operation arbitrary load ratio time according to the height of ash oontent in the raw material and original carbon black extraction process, the handiness and the reliability of whole carbon black water treatment device operation have been improved greatly, carry out supportingly for adopting mixing oil to do vapourizing furnace that raw material carries out partial oxidation gas, obtained good effect.
At last; the nozzle of vapourizing furnace is that the nozzle cooling tube is watered all-in-one-piece together with the fuel oil urceolus with high-density refractory casting material; it has protected nozzle head to be subjected to the ablation of high-temperature gas well; and reduction burner cooling backwater temperature; make the fire box temperature of vapourizing furnace can reach 1400-1450 ℃; avoid because the rapid accumulation of metal in the vapourizing furnace combustion chamber such as the aluminium that brings of mixing oil, silicon, prolonged the operational cycle of vapourizing furnace.
Examples of implementation 2:
Mixing oil adopts at the bottom of 60 (wt) % de-oiled asphalt and 30 (wt) % tower oil and 10 (wt) % washing oil that often reduces pressure.
The vapourizing furnace temperature in enters the gasification zone with mixing oil by the multi-nozzle vapourizing furnace under 270 ℃ condition, make mixing oil in the viscosity of vapourizing furnace ingress about 30 centipoises, to obtain good atomizing effect.Other is similar to examples of implementation 1.
Examples of implementation 3:
Oil at the bottom of mixing oil employing 80 (wt) % de-oiled asphalt and 20 (wt) % tower, perhaps vacuum residuum, often reduce pressure washing oil, thermal cracking residue and their mixtures thereof, the feeding preheating device has been installed before the vapourizing furnace, and that mixing oil is brought up to is the highest 270 ℃, make the vapourizing furnace temperature under 270 ℃ suitable condition, mixing oil be entered the gasification zone by the multi-nozzle vapourizing furnace, to obtain good atomizing effect.Other is similar to examples of implementation 1.
Examples of implementation 4:
Oil at the bottom of mixing oil employing 95 (wt) % de-oiled asphalt and 5 (wt) % tower, perhaps vacuum residuum, often reduce pressure washing oil, thermal cracking residue and their mixtures thereof, the feeding preheating device has been installed before the vapourizing furnace, and that mixing oil is brought up to is the highest 310 ℃, make the vapourizing furnace temperature under 280 ℃ suitable condition, mixing oil be entered the gasification zone by the multi-nozzle vapourizing furnace, to obtain good atomizing effect.Other is similar to examples of implementation 1.
Examples of implementation 5:
Oil at the bottom of mixing oil employing 70 (wt) % de-oiled asphalt and 30 (wt) % tower, perhaps vacuum residuum, often reduce pressure washing oil, thermal cracking residue and their mixtures thereof, the feeding preheating device has been installed before the vapourizing furnace, and that mixing oil is brought up to is the highest 240 ℃, make the vapourizing furnace temperature under 240 ℃ suitable condition, mixing oil be entered the gasification zone by the multi-nozzle vapourizing furnace, to obtain good atomizing effect.Other is similar to examples of implementation 1.
Examples of implementation 6:
Oil at the bottom of mixing oil employing 80 (wt) % de-oiled asphalt and 20 (wt) % tower, perhaps vacuum residuum, often reduce pressure washing oil, thermal cracking residue and their mixtures thereof, the feeding preheating device has been installed before the vapourizing furnace, and that mixing oil is brought up to is the highest 250 ℃, make the vapourizing furnace temperature under 250 ℃ suitable condition, mixing oil be entered the gasification zone by the multi-nozzle vapourizing furnace, to obtain good atomizing effect.Other is similar to examples of implementation 1.
Claims (12)
1, a kind of method of overweight mixing oil gasification production synthetic gas inferior, it infeeds the gasification zone with oxygen-containing gas, mixing oil and optional moderator gas, carry out partial oxidation, it is characterized in that described mixing oil, at least comprise de-oiled asphalt 60-95 (wt) % that produces through solvent deasphalting unit and slurry oil 5-30 (wt) % that produces through catalytic cracking unit, be under 240-280 ℃ the suitable condition in the gasifying furnace nozzle temperature in, mixing oil is entered the gasification zone by the multi-nozzle vapourizing furnace, in 1400-1450 ℃ of scope, carry out partial oxidation.
2, the method for production synthetic gas according to claim 1 is characterized in that described gasifying furnace nozzle temperature in is 260-265 ℃.
3, the method for production synthetic gas according to claim 1 is characterized in that described de-oiled asphalt is the Cn-pitch that mixed residue oil obtains from the solvent deasphalting technological process, n is 3,4,5 or bigger.
4, the method for production synthetic gas according to claim 3 is characterized in that described solvent deasphalting technological process is to adopt C
4-supercritical extraction isolation technique, the extraction degree of depth of solvent deasphalting technological process are 45-75 (wt) %, are benchmark with the residual hydrocarbon total amount that enters the solvent deasphalting technological process.
5, the method for production synthetic gas according to claim 4 is characterized in that the residual oil of described residual hydrocarbon for obtaining from vacuum distillation apparatus.
6, the method for production synthetic gas according to claim 5 is characterized in that described slurry oil is to comprise that the stock oil of wax oil and mixtures of residua is through Residual oil that form and that be present in the catalysed fractionation tower bottom behind the catalytic cracking reaction.
7, the method for production synthetic gas according to claim 6, it is characterized in that having installed before the described vapourizing furnace feeding preheating device and make that the mixing oil temperature is the highest can not to surpass 280 ℃, mixing oil in the viscosity of gasifying furnace nozzle ingress in 20-40 centipoise scope.
8, the method for production synthetic gas according to claim 7 is characterized in that described Cn-pitch is mixed into mixing oil with slurry oil with solvent extraction through air-lift device again after containing solvent PPM rank.
9, the method for production synthetic gas according to claim 8, it is characterized in that its carbon black water that comes out of described vapourizing furnace is earlier through an interchanger, carry out heat exchange with the buck that returns the use of carbon black washing tower, reduce to 140～180 ℃, grey water temp then is increased to 180～210 ℃, reclaim high level heat, directly carry out the one-level flash distillation earlier, to remove process gas CO, the H that is dissolved in the carbon black water
2And H
2S guarantees in the postorder carbon black water no longer content toxic and harmful, further makes after the carbon black water for cooling simultaneously, carries out follow-up extraction treatment and/or sedimentation filtration treatment again.
10, the method for production synthetic gas according to claim 9 is characterized in that described interchanger adopts vertical tubular heat exchange capable of washing.
11, the method for production synthetic gas according to claim 10 is characterized in that adding wash-down water on the process gas pipeline of described vapourizing furnace outlet carries out spray irrigation, is provided with strainer in carbon black washing tower exit and filters.
12, the method for production synthetic gas according to claim 11 is characterized in that its nozzle of described vapourizing furnace is that the nozzle cooling tube is watered all-in-one-piece together with the fuel oil urceolus with high-density refractory casting material.
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| CN1955257B (en) * | 2005-10-24 | 2010-05-12 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical raw material |
| WO2011007231A2 (en) | 2009-07-17 | 2011-01-20 | Eni S.P.A. | Process and apparatus for the thermal treatment of refinery sludge |
| CN101979469A (en) * | 2010-11-17 | 2011-02-23 | 湖南长岭石化科技开发有限公司 | Method for removing free oxygen from inferior hydrogenation raw oil |
| CN102234536A (en) * | 2010-05-07 | 2011-11-09 | 中国石油化工股份有限公司 | Combined technology for processing heavy oil |
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| US4483690A (en) * | 1982-06-07 | 1984-11-20 | Texaco Development Corporation | Apparatus for production of synthesis gas from heavy hydrocarbon fuels containing high metal concentrations |
| CN1056817C (en) * | 1993-04-08 | 2000-09-27 | 国际壳牌研究有限公司 | A process for partial oxidation of a hydrocarboncontaining fuel |
| JPH07286183A (en) * | 1994-03-22 | 1995-10-31 | Shell Internatl Res Maatschappij Bv | Method for conversion of hydrocarbon bottom oil |
| CN1163572C (en) * | 1998-07-29 | 2004-08-25 | 德士古发展公司 | Integration of solvent deasphalting and gasification |
| JP2003268389A (en) * | 2002-03-14 | 2003-09-25 | Nittetsu Gijutsu Joho Center:Kk | Method for gasification of sulfur-containing carbonaceous material or sulfur-containing hydrocarbon |
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| WO2011007231A2 (en) | 2009-07-17 | 2011-01-20 | Eni S.P.A. | Process and apparatus for the thermal treatment of refinery sludge |
| CN102234536A (en) * | 2010-05-07 | 2011-11-09 | 中国石油化工股份有限公司 | Combined technology for processing heavy oil |
| CN102234536B (en) * | 2010-05-07 | 2014-10-22 | 中国石油化工股份有限公司 | Combined technology for processing heavy oil |
| CN101979469A (en) * | 2010-11-17 | 2011-02-23 | 湖南长岭石化科技开发有限公司 | Method for removing free oxygen from inferior hydrogenation raw oil |
| CN101979469B (en) * | 2010-11-17 | 2013-05-15 | 湖南长岭石化科技开发有限公司 | Method for removing free oxygen from inferior hydrogenation raw oil |
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| US10208950B2 (en) | 2013-10-03 | 2019-02-19 | Eni S.P.A. | Waste sludge incinerator using pyrolysis and gasification, and relative process |
| CN108203602A (en) * | 2016-12-19 | 2018-06-26 | 中国石油天然气股份有限公司 | Heavy oil modification process unit |
| CN108286714A (en) * | 2018-03-27 | 2018-07-17 | 吉林北沙制药有限公司 | A kind of chemical waste liquid burning disposal method of comprehensive utilization and system |
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Owner name: CHINA PETROLEUM CHEMICALS CO., LTD. TOWN HAI LIAN Free format text: FORMER NAME OR ADDRESS: ZHENHAI OIL-REFINING CHEMICALCO., LTD., CHINA PETRO-CHEMICAL CORP. |
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Address after: 315207 Zhenhai Zhenhai Refining & Chemical Branch Company, Zhenhai District, Zhejiang, Ningbo Patentee after: SINOPEC ZHENHAI REFINING & CHEMICAL CO. Address before: 315207 Zhenhai Zhenhai Refining and chemical Limited by Share Ltd, Zhenhai District, Zhejiang, Ningbo Province, China Patentee before: SINOPEC Zhenhai Refining & Chemical Co.,Ltd. |
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Granted publication date: 20070117 |