CN1053002C

CN1053002C - Process for improving high-sulfur emulsible oil to low-sulfur emulsible oil

Info

Publication number: CN1053002C
Application number: CN96117216A
Authority: CN
Inventors: 林榕
Original assignee: Individual
Current assignee: Individual
Priority date: 1996-12-17
Filing date: 1996-12-17
Publication date: 2000-05-31
Anticipated expiration: 2016-12-17
Also published as: CN1185478A

Abstract

The present invention relates to a technology for improving high sulfur emulsified oil into low sulfur emulsified oil. The present invention is characterized in that low sulfur heavy crude oil or heavy oil (residual oil) is used for diluting high sulfur Aioli emulsified oil for reducing the sulfur content; water and emulsifying agents are added for emulsifying and synthesizing low sulfur emulsified oil again. The present invention has the advantages that except for emulsified fuel oil, the present invention has the characteristics of low heating value higher than that of high sulfur Aioli emulsified oil and sulfur content smaller than or equal to 1%, breaks through the defect that Aioli emulsified oil is used for heat power electricity generation needing many investments for combustion and desulphurization discharge, starts a method for accelerating the use of international economy type Aioli emulsified oil, offsets the shortage of combustion oil, propels oil saving, improves environment protection and has very important significance.

Description

Improvement high-sulfur oil in water emulsion is the technology of low-sulfur oil in water emulsion

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

Sequence number	Title	Symbol	Unit	No. 200 heavy oil	Add water 44%	Add water 40%
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	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	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

2, the calorific value of homemade No. 200 heavy oil and oil in water emulsion thereof

Fuel	No. 200 heavy oil	Add water 40%	Add water 44%
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

3, the heavy oil of two states is formed

Composition (%)	C	H	O	S	W	N
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	Before the water mixing	83.37	11.41	0.68	0.21	4.04	0.29

4, the exhaust gas components of two states

Composition (%)	RO ₂	CO	O ₂	CH ₄	H ₂	N ₂
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	-	-	Before the water mixing	12.10	0.95	7.5	0.14	-	-

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. 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.