CN1053002C - Process for improving high-sulfur emulsible oil to low-sulfur emulsible oil - Google Patents
Process for improving high-sulfur emulsible oil to low-sulfur emulsible oil Download PDFInfo
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- CN1053002C CN1053002C CN96117216A CN96117216A CN1053002C CN 1053002 C CN1053002 C CN 1053002C CN 96117216 A CN96117216 A CN 96117216A CN 96117216 A CN96117216 A CN 96117216A CN 1053002 C CN1053002 C CN 1053002C
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- Prior art keywords
- oil
- sulfur
- low
- emulsified
- water
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title abstract description 6
- 230000008569 process Effects 0.000 title abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010779 crude oil Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000007764 o/w emulsion Substances 0.000 claims description 15
- 238000004945 emulsification Methods 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000004996 alkyl benzenes Chemical class 0.000 claims 1
- 150000002632 lipids Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 30
- 239000000295 fuel oil Substances 0.000 abstract description 27
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 239000000446 fuel Substances 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 6
- 230000023556 desulfurization Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000010248 power generation Methods 0.000 abstract description 2
- 241000772415 Neovison vison Species 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 7
- 239000003245 coal Substances 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- -1 sodium alkyl benzene Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002210 biocatalytic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种改良高硫乳化油为低硫乳化油的工艺，其特征是采用低硫重质原油或重油(渣油)稀释高硫“奥里乳化油”，降低硫含量，再加水和乳化剂，重新乳化合成低硫乳化油。其优点除具备“乳化燃料油”外，还具有低位发热量高于高硫“奥里乳化油”，硫含量≤1%的特点。它突破了至今使用“奥里乳化油”火力发电，均须投巨资燃烧后脱硫排放的困扰，开创了加快利用国际经济型“奥里乳化油”，弥补燃料油短缺，推进节油及改善环保有着十分重要的意义。A process for improving high-sulfur emulsified oil into low-sulfur emulsified oil, which is characterized in that low-sulfur heavy crude oil or heavy oil (residual oil) is used to dilute high-sulfur "Oli emulsified oil" to reduce the sulfur content, and then add water and emulsifier, Re-emulsify synthetic low-sulfur emulsified oil. In addition to its advantages of "emulsified fuel oil", it also has the characteristics of low calorific value higher than high-sulfur "Oli emulsified oil", and the sulfur content is less than or equal to 1%. It breaks through the problem of using "Oli emulsified oil" thermal power generation, which requires huge investment in desulfurization emissions after combustion, and creates an accelerated use of international economical "Oli emulsified oil" to make up for the shortage of fuel oil, promote fuel saving and improve Environmental protection is of great significance.
Description
The invention belongs to high sulphur fuel oil emulsification, combustion desulfurization technology field.
High-sulfur " emulsified orinoco crude oil " is generally with 70% heavy rock asphalt and 30% water and additive emulsification synthetic emulsified fuel oil, its performance is better than general heavy oil and coal, particularly its burning fully, the dust of discharging is than burning the coal much less, and no acidic dust, be difficult for producing acid rain, unburned hydrocarbon also lacks than general oil firing in the discharge.Reach more than 8,600,000,000 tons because it verifies the exploitation reserves, enrich and be world-famous for so contain with heavy oil.In the international market, its price and coal are similar, but the obstacle that perplexs its broad practice so far is because of its unit base sulphur content reaches 2.7%, according to international environmental requirement, reach SO
2Emission standard all need be thrown huge fund construction burning back desulfurization discharge equipment.Having only minority industrially developed country to throw huge fund at present uses high-sulfur " emulsified orinoco crude oil " as power generation applications.
The objective of the invention is to avoid the weak point that above-mentioned prior art exists and provide a kind of cost of investment low, operation is simple, and can implement in enormous quantities, reduce the basic sulphur content of high-sulfur " emulsified orinoco crude oil ", make its before burning just improvement be the novel process of≤1% low-sulfur oil in water emulsion.
Purpose of the present invention can reach by following measure:
A kind ofly improve the technology that the high-sulfur oil in water emulsion is the low-sulfur oil in water emulsion, it is characterized in that adopting low sulfur heavy crude oil or heavy oil (residual oil) dilution high-sulfur " emulsified orinoco crude oil ", reduce sulphur content, add water and emulsifying agent again, again the synthetic low-sulfur oil in water emulsion (sulphur content≤1%) of emulsification.
Purpose of the present invention can also reach by following measure:
Above-mentioned material proportion is: low sulfur heavy crude oil or heavy oil (residual oil): high-sulfur " emulsified orinoco crude oil ": water: emulsifying agent=55-65%: 30%: 10-15%: 0.2-0.3%;
Low sulfur heavy crude oil or heavy oil (residual oil) sulphur content≤0.3%;
Emulsifying agent adopts sodium soap or sodium alkyl benzene sulfonate.
The sulphur, emulsification, flame mechanism of falling of the present invention is:
High-sulfur " emulsified orinoco crude oil " is different in form in emulsification with general emulsified fuel oil, the first " oil-in-water-type ", and oil droplet is surrounded by tensio-active agent, forms the hydrophilic interface film wrapped, and water is external phase, and oil is disperse phase.It two is " water-in-oil-types ", and water droplet is surrounded by tensio-active agent, forms oleophylic interfacial film parcel, and oil is external phase, and water is disperse phase.But its flame mechanism is identical: when emulsion fuel when nozzles spray, be the about 60-120 μ of diameter m particulate immediate status.Because the burner hearth certain high temperature, wherein the water particulate heats up rapidly and vaporizes, and volume sharply expands and produces hundreds of and even several thousand barometric points, and moment pops oil droplet, becomes the littler fine oil droplet of numerous diameters.Because this process carries out to such an extent that be exceedingly fast, thus be called " microexplosion " or " secondary-atomizing ", thus increased the contact surface with air, realized perfect combustion, reduced oil consumption, reached the purpose of fuel-economizing.In addition, because water has participated in the incendiary chemical reaction, combustionvelocity is accelerated, overheavy firing impels sufficient combustion.
Response procedures the when anhydrous: (C in the reaction formula
mH
nExpression mink cell focus molecule)
As if having water vapour to mix with CO in boiler and reacting, combustion reactions will more promptly be carried out by following program:
This shows, do not containing H
2When the CO of O burns, superfluous oxygen must be arranged, and containing H
2When the CO of O burns, can produce certain H
2, therefore improved combustion efficacy, improved temperature of combustion, increased boiler efficiency.Simultaneously, when having realized the emulsion fuel oil firing, there is not unburnt fervid carbon granules yet.Under the situation that has aqueous vapor to exist, the fume amount of tail gas is descended greatly, reduced environmental pollution.
Can be energy-conservation in order to allow people fully realize to use emulsion fuel, especially to being difficult to the fuel-economizing of atomized heavy oil emulsification, combustion, and the Practical significance of improving environmental protection, Tsing-Hua University in 9 years " China energy " magazine third phases, delivered relevant experimental result and analysis:
1, homemade No. 200 heavy oil and the main result of emulsification, combustion hot test thereof
2, the calorific value of homemade No. 200 heavy oil and oil in water emulsion thereof
3, the heavy oil of two states is formed
4, the exhaust gas components of two states
| Sequence number | Title | Symbol | Unit | No. 200 heavy oil | Add water 44% | Add water 40% |
| 1 | The output quantity of steam | D | kg/h | 670 | 532 | 670 |
| 2 | Fuel consumption | B | kg/h | 51 | 46 | 56 |
| 3 | Counter-balance thermal efficiency | 7 | ％ | 79.8 | 79.9 | 81.5 |
| 4 | The boiler quantity of heat given up | Q | kJ/h | 1.683×10 6 | 1.33×10 6 | 1.69×10 6 |
| 5 | The equivalent heat value of calculating | Qr | kJ/kg kcal/kg | 41361 9895 | 36186 8657 | 37022 8859 |
| Fuel | No. 200 heavy oil | Add water 40% | Add water 44% |
| kcal/kg kJ/kg | 9967.6 40535.9 | 4116.9 29748.6 | 6907 28871.3 |
| Composition (%) | C | H | O | S | W | N |
| Before the water mixing | 83.37 | 11.41 | 0.68 | 0.21 | 4.04 | 0.29 |
| After the water mixing | 76.21 | 8.60 | 0.70 | 0.20 | 14.00 | 0.29 |
| Composition (%) | RO 2 | CO | O 2 | CH 4 | H 2 | N 2 |
| Before the water mixing | 12.10 | 0.95 | 7.5 | 0.14 | - | - |
| After the water mixing | 12.97 | 0.42 | 7.1 | 0.09 | - | - |
Result's demonstration shows that the prior meaning of emulsion fuel incendiary is not only in fuel-economizing, but in environmental protection, this is crucial to 21 century, and prediction emulsion fuel incendiary upsurge will arrive once more.
The present invention has following advantage compared to existing technology:
The present invention proposes to rely on the general a large amount of low-sulfur mink cell focuses (being heavy crude, heavy oil, residual oil) that use of present society, dilute the mode of " emulsified orinoco crude oil " basic sulphur content of high sulfur-bearing, sulphuring treatment falls in realization, has overcome the problem of existing hydrogenating desulfurization and biocatalytic desulfurization facility investment expense costliness.
Because " emulsified orinoco crude oil " in a single day mixes with other oil, will make its water film breaks, oil droplet reassembles, and causes " emulsified orinoco crude oil " sex change, breakdown of emulsion, oily water separation.For adhering to bringing into play the advantage of burning oil in water emulsion so select employing rationally to add water and corresponding emulsifying agent once more, according to the proportioning of burning " oil in water emulsion " optimal performance, emulsification is synthetic, contains the low-sulfur emulsified fuel oil of " oli oil ".
Low-sulfur emulsified fuel oil provided by the invention not only meets the existing boiler design manufacturing of China, the requirement of anticorrosion safety coefficient range fuels oil base sulphur≤1%, and also its burning back desulfurization discharging facility also is what to have possessed, need not increase.
Sulphur is in oil fuel, and most of form with organic sulfide exists, and originally can burn.But products of combustion has outside the corrosive nature boiler plant, also to environment and human body harmful.And general heavy oil of emulsion fuel oil ratio and coal have above-mentioned " microexplosion " effect on combustionproperty, and it can fully be burnt, and put flue SO
2Content than direct burning heavy oil lack many, it more is of value to the minimizing environmental pollution.
In addition, " emulsified orinoco crude oil " stipulates that other oil product mixed volume must not surpass 2% in storage and transport process, require oil tank, boats and ships to clean, and pipeline will be established the pigging facility.This is not to generally using the market of " emulsified orinoco crude oil ", so accumulating, can bring inconvenience and increase the accumulating expense, and cause bring down stocks oil waste, and the present invention has the versatility of all mink cell focuses of accumulating, simultaneously, also bring glad tidings for utilizing again after the big ship that comes to pick up goods, the unloaded Cang Shui of the pressure discharging.
Therefore, adopting the present invention be the low-sulfur emulsified fuel oil for improvement high-sulfur " emulsified orinoco crude oil ", and quickens digestion and introduce use international economy type " emulsified orinoco crude oil ", remedies Chinese oil fuel shortage, economizes on oil, improves environmental protection and started a new way.Also for from now on, worldwide extensive improved application high-sulfur " emulsified orinoco crude oil " advances fuel-economizing and improves environmental protection crucial meaning simultaneously.
Embodiment:
One, emulsification processing ratio and measuring and calculating: low-sulfur mink cell focus: high-sulfur oil in water emulsion: water: emulsifying agent=60-55%: 30%: 10-15%: 0.2-0.3%
The low-sulfur mink cell focus is meant sulfur-bearing＜below 0.5%, density＞0.9g/cm
320 ℃ low sulfur heavy crude oil, heavy oil (residual oil);
The high-sulfur oil in water emulsion mainly refers to " emulsified orinoco crude oil " that Venezuela state produces;
Emulsifying agent is meant that sodium soap or sodium alkyl benzene sulfonate are the additive of major ingredient.
Concrete determination of ratio is to decide flexibly with the sulphur content of low-sulfur mink cell focus.Be higher than at 0.3% o'clock as low-sulfur mink cell focus sulfur-bearing, just by-election is allocated dilution, is dropped into the mink cell focus of some amount sulfur-bearing≤0.2%.
Two, emulsifying manner: can use mechanical systems such as heavy oil emulsive pump or emulsifying collid mill, also can adopt hyperacoustic mode.
Three, emulsifying temperature is controlled at 60 ℃-70 ℃.
Four, emulsification synthesis step:
The low-sulfur mink cell focus adds the high-sulfur mink cell focus, and water adds emulsifying agent, and both enter emulsification pump and realize emulsification then, warehouse-in.
Five, its technical indicator of low-sulfur oil in water emulsion after the emulsification processing is:
1, sulphur content≤1%;
2, equivalent heat value 〉=8000 kilocalorie/kilograms;
3, counter-balance thermal efficiency 〉=80%;
4, stable emulsifying time＞180 day;
5, flash-point (opening) ℃ is not less than 80 ℃;
6, condensation point ℃ is not higher than 26 ℃;
7, kinematic viscosity E50 ℃ is not more than 200 centistokes.
Claims (1)
1. improve the technology that the high-sulfur oil in water emulsion is the low-sulfur oil in water emulsion for one kind, it is characterized in that adopting low sulfur heavy crude oil or low sulfur resid dilution high-sulfur " emulsified orinoco crude oil ", reduce sulphur content, add water and emulsifying agent again, again the low-sulfur oil in water emulsion of its sulphur content≤1% is synthesized in emulsification, above-mentioned material proportion is: low sulfur heavy crude oil or low sulfur resid: high-sulfur " emulsified orinoco crude oil ": water: emulsifying agent=55-65%: 30%: 10-15%:0.2-0.3%, the sulphur content of described low sulfur heavy crude oil or low sulfur resid≤0.3%; Emulsifying agent adopts lipid acid to receive or alkyl benzene sulphonate (ABS) is received.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117216A CN1053002C (en) | 1996-12-17 | 1996-12-17 | Process for improving high-sulfur emulsible oil to low-sulfur emulsible oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96117216A CN1053002C (en) | 1996-12-17 | 1996-12-17 | Process for improving high-sulfur emulsible oil to low-sulfur emulsible oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1185478A CN1185478A (en) | 1998-06-24 |
| CN1053002C true CN1053002C (en) | 2000-05-31 |
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ID=5124148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96117216A Expired - Fee Related CN1053002C (en) | 1996-12-17 | 1996-12-17 | Process for improving high-sulfur emulsible oil to low-sulfur emulsible oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053002C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498082A (en) * | 2014-12-30 | 2015-04-08 | 江苏健神生物农化有限公司 | Preparation method for environment-friendly fuel from hydrodesulfurized residue oil |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5134846A (en) * | 1974-09-18 | 1976-03-24 | Hitachi Ltd | MAKITORIMAKI DASHIKINODORAMU |
| JPS5134846B2 (en) * | 1972-05-13 | 1976-09-29 | ||
| JPS5884895A (en) * | 1981-11-17 | 1983-05-21 | Fuji Eng Kk | Emulsion fuel manufacturing method |
| CN1083515A (en) * | 1993-09-14 | 1994-03-09 | 程国柱 | A kind of modified emulsion fuel oil and production method thereof |
| JPH06108072A (en) * | 1992-09-24 | 1994-04-19 | Kao Corp | Method for producing heavy oil emulsion fuel |
| JPH06240267A (en) * | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Emulsified fuel oil composition |
| CN1107503A (en) * | 1994-12-26 | 1995-08-30 | 黄行声 | Emulsified fuel by blending water with heavy oil- double-base heavy oil |
-
1996
- 1996-12-17 CN CN96117216A patent/CN1053002C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5134846B2 (en) * | 1972-05-13 | 1976-09-29 | ||
| JPS5134846A (en) * | 1974-09-18 | 1976-03-24 | Hitachi Ltd | MAKITORIMAKI DASHIKINODORAMU |
| JPS5884895A (en) * | 1981-11-17 | 1983-05-21 | Fuji Eng Kk | Emulsion fuel manufacturing method |
| JPH06108072A (en) * | 1992-09-24 | 1994-04-19 | Kao Corp | Method for producing heavy oil emulsion fuel |
| JPH06240267A (en) * | 1993-02-19 | 1994-08-30 | Mitsubishi Petrochem Co Ltd | Emulsified fuel oil composition |
| CN1083515A (en) * | 1993-09-14 | 1994-03-09 | 程国柱 | A kind of modified emulsion fuel oil and production method thereof |
| CN1107503A (en) * | 1994-12-26 | 1995-08-30 | 黄行声 | Emulsified fuel by blending water with heavy oil- double-base heavy oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1185478A (en) | 1998-06-24 |
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