CN101553553A - Process for upgrading heavy hydrocarbon oils - Google Patents
Process for upgrading heavy hydrocarbon oils Download PDFInfo
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- CN101553553A CN101553553A CNA2007800403123A CN200780040312A CN101553553A CN 101553553 A CN101553553 A CN 101553553A CN A2007800403123 A CNA2007800403123 A CN A2007800403123A CN 200780040312 A CN200780040312 A CN 200780040312A CN 101553553 A CN101553553 A CN 101553553A
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 59
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 59
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 59
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 27
- 239000010779 crude oil Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000011269 tar Substances 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 4
- 239000011275 tar sand Substances 0.000 claims description 4
- 239000011280 coal tar Substances 0.000 claims description 3
- -1 vacuum residuum Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 239000000376 reactant Substances 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000008186 active pharmaceutical agent Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 21
- 239000005864 Sulphur Substances 0.000 description 16
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- 241000772415 Neovison vison Species 0.000 description 11
- 230000005484 gravity Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 238000004517 catalytic hydrocracking Methods 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/047—Hot water or cold water extraction processes
Abstract
A process using supercritical water to upgrade a heavy hydrocarbon feedstock into an upgraded hydrocarbon product or syncrude with highly desirable properties (low sulfur content, low metals content, lower density (higher API), lower viscosity lower, residuum content, etc.) is disclosed. The process does not require external supply of hydrogen nor does it use externally supplied catalysts. Improved methods of mixing the reactants are also disclosed.
Description
Invention field
The present invention relates to use supercritical water that for example full cut heavy oil of heavy hydrocarbon, pitch etc. are carried out upgrading.
Background of invention
To such an extent as to the oil that is produced by all over the world big gauging deposit has weighed simply very much at ambient temperature and can not flow.This makes remote heavy oil resources more become challenge near market.The Hamaca field with "nine squares" that typical example is Venezuela.For making this type of mink cell focus to flow, one of prevailing method known in the art is by mink cell focus and competent mixing diluents are reduced viscosity and density.Described thinner can be petroleum naphtha or have any other logistics of the api gravity (be much lower density) significantly higher than described mink cell focus.
For the situation of for example Hamaca, the crude oil that has diluted is delivered to the upgrading equipment via pipeline from production wellhead.Have two key operations in described upgrading equipment: (1) is reclaimed described diluent stream and in independent pipeline it is looped back production wellhead, and (2) make described heavy-oil modifiedly with suitable technique as known in the art (coking, hydrocracking, hydrotreatment etc.), is that market produces the product of higher value.Some characteristic features of the product of these higher values comprise: lower sulphur content, lower metal content, lower total acid value (TAN), lower residue content, higher api gravity and lower viscosity.By making described mink cell focus and hydrogen in the presence of catalyzer, react the great majority that obtain in these features of wanting under the high temperature and high pressure.Under the situation of Hamaca, the crude oil of upgrading further is transported to end user location via tank car.
These thinners add/remove method and hydrogenation or other method for modifying and have many shortcomings:
1. the needed Infrastructure of processing, recovery and recycle diluent is expensive, especially for the situation of growing distance.The availability of thinner is another potential problem.
2. for example hydrotreatment or hydrocracking need a large amount of investments to method of hydrotreating on capital and Infrastructure.
3. method of hydrotreating also has high running cost, because the cost that produces hydrogen is extremely sensitive for the price of Sweet natural gas.The mink cell focus deposit that some are remote even the low-cost Sweet natural gas that may keep clear of q.s are to support hydrogen device.These method of hydrotreating also need expensive catalysts and resource-intensive catalyst treatment technology usually, comprise catalyst regeneration.
4. in some cases, nearest refining and/or the upgrading equipment in the described production of distance place may neither have the equipment that the ability that receives described mink cell focus does not have the described mink cell focus of reception yet.
5. usually in refining or upgrading equipment, use coking technology.Abandon a large amount of by-product solid coke in described coking, this causes lower liquid hydrocarbon yield.In addition, the product liquid from the coke-oven plant usually needs further hydrotreatment.And, from the volume of the product of coking significantly less than the volume of feed crude oil.
The method according to this invention is that the hydrocarbon product or the synthetic crude of the upgrading of performance (low sulfur content, low-metal content, lower density (higher API), lower viscosity, lower residue content etc.) with high desirability overcome these shortcomings with the heavy hydrocarbon feedstocks upgrading by using supercritical water.Described method neither needs outside hydrogen supply neither use catalyzer.In addition, method of the present invention does not produce considerable coke by-product.
Compare with traditional synthetic crude production method, the advantage that can obtain by enforcement the present invention comprises high liquid hydrocarbon yield; The hydrogen that does not need outside supply; Do not need to provide catalyzer; Improve the api gravity of the hydrocarbon product of upgrading greatly; Significantly reduce the viscosity of the hydrocarbon product of upgrading; And significantly reduce sulphur, metal, nitrogen, TAN and MCR (little carbon residue) in the hydrocarbon product of upgrading.
The several different methods of using the supercritical water treatment heavy hydrocarbon is disclosed in the patent documentation.Example comprises United States Patent (USP) sequence number 3,948,754; 3,948,755; 3,960,706; 3,983,027; 3,988,238; 3,989,618; 4,005,005; 4,151,068; 4,557,820; 4,559,127; 4,594,141; 4,840,725; 5,611,915; 5,914,031 and 6,887,369 and European patent 671454.
United States Patent (USP) sequence number 4,840,725 discloses uses supercritical water that the high boiling liquid organic materials is converted into the more method of lower boiling material in tubular flow reactor.Described water and hydrocarbon preheating respectively also just mixed in the high pressure feedstock pump before described reactor is given in charging.
United States Patent (USP) sequence number 5,914,031 discloses three district's reactor design so that make the optimization respectively that is separated of reactant activity, reactant solubility and product by controlled temperature and pressure.Yet all embodiment that provide in this patent are to use periodical operation to obtain.
United States Patent (USP) sequence number 6,887,369 discloses the preferred supercritical water pretreatment process that uses hydrogen or carbon monoxide to carry out and has come hydrotreatment and hydrocracking carbonaceous material in deep well reactor.Described deep well reactor transformation is from underground oil wells, and is made up of a plurality of concentric tubes.The deep well reactor of describing in this patent is by being incorporated into feed stream the core pipe and operating at outer ring shape part Returning reactor effluent.
Except that above-mentioned factor, the present invention is based in following experiment and find: reactant heating sequence promptly oily and water is vital to obtaining enhanced upgrading performance, this means to reduce or eliminate by product for example solid residue and light hydrocarbon gas.Reduce the solid generation and not only improved the liquid oils yield, also allow to make described method more effectively to operate.As everyone knows, the solid in the system can bring remarkable challenge to reactor and technological design.The direct heating of oil raw material may cause superheated, thereby causes more solid residue to generate the yield of the lower product of wanting and lower product quality.
Summary of the invention
The present invention relates to hydrocarbon, preferred heavy hydrocarbon are carried out the method for upgrading, comprising: hydrocarbon is heated to the fluid that temperature is higher than the water of its critical temperature and mixes in the mixing zone with the formation mixture with comprising; Described mixture is passed to reaction zone; Described mixture is not reacted under the situation of hydrogenation outside having under condition of supercritical water in described reaction zone, and the residence time is enough to allow the upgrading reaction to take place; Take out the homogeneous reaction product from described reaction zone; And the hydrocarbon phase that described reaction product is divided into gas phase, effluent water and upgrading.
The accompanying drawing summary
Fig. 1 is the process flow sheet of one embodiment of the invention.
Fig. 2 is the process flow sheet of another embodiment of the invention.
Fig. 3 shows desired T
SCWFigure as the function of water/oil ratio.
Fig. 4 is the process flow sheet of another embodiment of the invention.
Embodiment preferred is described
Reactant
Water and hydrocarbon, preferred heavy hydrocarbon is two kinds of reactants that use in the method according to this invention.
Any heavy hydrocarbon can carry out suitable upgrading by the method according to this invention.Preferred api gravity is less than 20 ° heavy hydrocarbon.Heavy hydrocarbon, heavy crude crude oil example such as the Venezuela Orinoco mink cell focus band crude oil that wherein preferred heavy hydrocarbon is heavy crude, extract from Tar sands (be commonly referred to tar sand bitumen, for example obtain from Canadian Athabasca tar sand bitumen), Boscan mink cell focus, acquisition are from the heavy hydrocarbon fractions of petroleum crude oil particularly heavy vacuum gas oil, vacuum residuum and petroleum tar, Tar sands and coal tar.Other example of operable heavy hydrocarbon feedstocks is resinous shale, shale oil and bituminous matter.
Water
Can in the aqueous fluid of described bag, use the water in any source in the embodiment of this invention.The source of water includes but not limited to the water that waste water tap water, processing or not processed, river, lake water, seawater are produced etc.
Mix
According to the present invention, heavy hydrocarbon feedstocks is heated to the fluid that temperature is higher than the water of its critical temperature and contacted in the mixing zone before entering described reaction zone with comprising.According to the present invention, can finish in many ways and mix and preferably finish by the technology of not using mechanical displacement means.This type of mixing device can include but not limited to the use of static mixer, spray nozzle, sound or ultrasonic agitation.Should heat and mix described oil and water so that the logistics that has mixed reaches condition of supercritical water in reaction zone.
Discovery has significantly reduced for example formation of solid residue of by product by avoiding the described stock oil of superheated.A critical aspects of the present invention is that the design heating sequence is so that the temperature and pressure of described hydrocarbon and water reaches reaction conditions with controllable mode.This can be avoided the local excessive heating of oil, and the local excessive heating can cause solid to form and more inferior product.For obtaining better properties, described oil should only lean on the water of the q.s that exists around the described hydrocarbon molecule to heat.Can reach this requirement by before heating, oil being mixed with water.
Fig. 2 is the process flow sheet of one embodiment of the invention.In this embodiment, water is heated to above the temperature of its critical condition, and mixes with oil then.It is interior to avoid thermally splitting that the temperature of heavy oil feed should maintain about 100 ℃～200 ℃ scopes, still still enough high to keep rational pressure drop.The temperature of described water logistics should be enough high with guarantee with oily the mixing after, the temperature of described oil-water mixture is still than the supercritical temperature height of water.In this embodiment, in fact heat described oil by water.Large quantity of moisture around described hydrocarbon molecule can suppress the formation that therefore condensation reaction also reduces coke and solid product greatly.
The temperature T of desired supercritical water stream
SCW, can be based on temperature of reaction T
RAnd water/oil ratio is estimated.Because the thermal capacitance of water is very big in the scope inner conversion near its critical condition, for given temperature of reaction, the temperature of desired supercritical water stream is along with the reduction of water/oil ratio almost raises by exponential relationship.Water/oil ratio is low more, T
SCWHigh more.Yet described relation is very nonlinear, because higher T
SCWCause lower thermal capacitance (away from stagnation point).Fig. 3 has shown as temperature of reaction T
RWhen=375 ℃ and pressure=3700psig as the desired T of the function of water/oil ratio
SCWIt should be noted that top temperature will be based on the character of specified raw material and determined.
Fig. 4 has shown according to another embodiment of the invention.By well heater 1 water is heated to super critical condition, in mixing tank, described supercritical water is mixed with heavy oil feed then.The temperature of described heavy oil feed should maintain in about 100 ℃～200 ℃ scopes, and is to avoid thermally splitting, still still enough high to keep rational pressure drop.After mink cell focus mixed, the temperature of water-oil mixture can be lower than the critical temperature of water; Therefore need well heater 2 temperature to be increased to the critical temperature that is higher than water with described mixture stream passes.In this embodiment, at first heat mink cell focus, by second well heater (well heater 2) water-oil mixture is heated to super critical condition then with water section.
It will be recognized by those skilled in the art, can use based on the mixing of above instruction and other method of heating sequence and finish these targets.
Reaction conditions
After described reactant mixes, make them enter reaction zone, in reaction zone, allow them under the temperature and pressure condition of supercritical water, promptly under the condition of supercritical water, outside having, not react under the situation of hydrogenation, the residence time is enough to allow the upgrading reaction to take place.The preferred permission taken place under the described situation that is reflected at no extra catalyst or promotor, although the use of this type of catalyzer and promotor allows according to the present invention.
" hydrogen " meaning in the phrase used herein " not having outer hydrogenation exists down " is a hydrogen.All hydrogen sources that can be used as reactant and obtain do not wanted to get rid of in this term.Other molecule for example stable hydrocarbon in reaction process by providing hydrogen to can be used as hydrogen source to other unsaturated hydrocarbons.In addition, steam reforming and the water-gas shift reaction by hydrocarbon can original position form H in described reaction process
2
Described reaction zone preferably comprises reactor, and this reactor is equipped with device and the preferred part in the bottom that is used for collecting reaction product (synthetic crude, water and gas), and this part can be gathered any metal or solid (" throw out logistics ").
Condition of supercritical water comprises 374 ℃ (critical temperatures of water)～1000 ℃, the temperature of preferred 374 ℃～600 ℃ and most preferably 374 ℃～400 ℃, 3205 (emergent pressure of water)～10000psia, preferred 3205～7200psia and the pressure of 3205～4000psia most preferably, and 1: 0.1～1: 10, the oil/water volume ratio of preferred 1: 0.5～1: 3 and most preferably from about 1: 1～1: 2.
Allowing described reactant to react under these conditions is enough to allow the time of upgrading reaction generation.Preferably, select the described residence time to allow described upgrading reaction preference ground and take place and to proceed to the degree of fullest and do not form the unacceptable side reaction of coke or residue.Reactor residence time can be 1 minute～6 hours, preferred 8 minutes～2 hours and most preferably 20～40 minutes.
Reaction product is separated
After reaction has fully been carried out, take out the homogeneous reaction product from described reaction zone, cooling also is divided into the hydrocarbon phase of gas phase, effluent water and upgrading with it.Preferably by cooling off described logistics and using one or more two phase separators, triphase separator or other gas-oil as known in the art-water separation equipment to finish described separation.Yet,, can use any separation method according to the present invention.
The composition of the gaseous product that obtains by the method according to this invention treatment of heavy hydrocarbon depends on feedstock property, and generally contain light hydrocarbon, water vapour, sour gas (CO
2And H
2S), methane and hydrogen.Described effluent water can use, reuse or is discarded.It for example can be recycled to raw material water tank, raw water treatment system or be recycled to described reaction zone.
Can use the hydrocarbon product of the known method in hydrocarbon processing field with described upgrading, this paper is called " synthetic crude " sometimes, further upgrading or be processed into other hydrocarbon product.
Method of the present invention can be carried out with continuous or semicontinuous method or discontinuous method or with the successive method.In continuation method, described total system adopts the feed stream of oil and independent supercritical water feed product to operate and reaches stable state; The composition of all thus flows, temperature, pressure and inlet, outlet and recycle stream does not have big variation in time.
Though be not bound by any theory of operation, it is believed that many upgrading reactions take place under the condition of supercritical water that uses in the method simultaneously.In the preferred embodiment of the invention, main chemistry/upgrading reaction is considered to:
Heat cracking reaction: C
xH
y→ lighter hydrocarbon
Steam reforming reaction: C
xH
y+ 2xH
2O=xCO
2+ (2x+y/2) H
2
Water-gas shift reaction: CO+H
2O=CO
2+ H
2
Demetalization reaction: C
xH
yNi
w+ H
2O/H
2→ NiO/Ni (OH)
2+ lighter hydrocarbon
Desulphurization reaction: C
xH
yS
z+ H
2O/H
2=H
2The hydrocarbon that S+ is lighter
Reactor operating condition (temperature, pressure, O/W volume ratio) may be depended in definite path, reactor design (contact/blended mode, the order of heating) and described hydrocarbon feed.
Following examples are of the present invention illustrating, but do not want to exceed any way restriction the present invention of the content that comprises in the following claim.
Embodiment 1-shows typical laboratory method
Fig. 1 has shown the process flow sheet of the lab setup that is used to implement embodiments more of the present invention.Oil contacted in mixing tank before entering described reactor with supercritical water.Described reactor is equipped with inner tube and the base section that is used to collect product (synthetic crude, excessive water and gas), can gather any metal or comprises character or form the solid of not clear " bottoms stream " at this base section.The shell-side of described reactor is kept isothermal with clamshell furnace and temperature regulator in reaction process.Preferred reactor residence time is 20～40 minutes, and preferred oil/water volume ratio is 1: 3 a rank.Preferred temperature is about 374～400 ℃, and pressure is 3200～4000psig.Described reactor product logistics is left with single-phase, and is cooled and is divided into gas, synthetic crude and effluent water.This reactor is returned in the recirculation of effluent water.Sulphur major part in the initial raw material accumulates in bottoms stream, less amount mainly with H
2The S form is present in gas phase and aqueous phase.
Show as next embodiment, produce very small amount of gas as a rule.Select suitable operational condition, also might reduce or almost eliminate described " bottoms stream ".Eliminate bottoms stream and mean that hydrocarbon is recovered as synthetic crude greatly, but it means that also metal and sulphur can for example in water and gas stream, gather in other place.
The character of embodiment 2-product synthetic crude
With ratio (thinners of 20 volume %s) the dilution Hamaca crude oil of thinner hydrocarbon with 5: 1.Measured its character make the Hamaca crude oil reaction of described dilution in the supercritical water process of being mentioned with embodiment 1 and Fig. 2 before.The character of described crude oil is as follows: at 60/60 time api gravity is that 12.8,40 ℃ of following viscosity are 1329CST; The C/H ratio of 7.66wt%; The MCRT of 13.04wt%; The sulphur of 3.54wt%; The nitrogen of 0.56wt%; 3.05mgKOH/gm acid number; The water of 1.41wt%; The vanadium of 371ppm; And the nickel of 86ppm.The Hamaca crude oil of described dilution is converted into synthetic crude after supercritical water treatment, this synthetic crude has following character: at 60/60 time api gravity is that 24.1,40 ℃ of following viscosity are 5.75CST; The C/H ratio of 7.40wt%; The MCRT of 2.25wt%; The sulphur of 2.83wt%; The nitrogen of 0.28wt%; 1.54mgKOH/gm acid number; The water of 0.96wt%; The vanadium of 24ppm; And the nickel of 3ppm.Observe metal and residue significantly reduces, improved api gravity simultaneously and significantly reduced the viscosity of original crude oil feedstock.Total acid value, sulphur concentration and nitrogen concentration have medium reduction, and this can improve by the further optimization of reaction conditions.
When the Hamaca of described dilution crude oil was directly delivered in the reactor and at first do not heated with supercritical water, described product synthetic crude has following character: at 60/60 time api gravity was that 14.0,40 ℃ of following viscosity are 188CST; The MCRT of 8.7wt%; The sulphur of 3.11wt%; The vanadium of 267ppm; And the nickel of 59ppm.This comparison shows that the importance of heating sequence of the present invention.
Except the small accumulation bottoms stream once in a while, in described supercritical water reaction, form considerably less coke or solid by-product.Material balance is carried out in two independent experiment operations.
In service in the experiment that does not have bottoms stream to form, the diluted Hamaca crude oil starting raw material of 60 grams produces 59.25 gram synthetic crude products, and this is corresponding to 99% high total yield.Think that the mass balance of experiment is subjected to the influence of the mensuration of sulphur and metal owing to there is not bottoms stream.Described gas phase is containing metal species and contain seldom sulphur compound not.Guess that a part of metal and sulphur may accumulate on the wall of reactor or downstream line.
In service in the experiment that has bottoms stream to form, the diluted Hamaca crude oil starting raw material of 30 grams produces 22.73 gram synthetic crude products.The bottoms stream that forms accounts for 5.5 grams.Add the above bottoms stream, total yield is 96.7%.In bottoms stream, sulphur accounts for 31% of whole sulphur, and all the other sulphur are in described oily product, water and gas phase.Metal content in the bottoms stream accounts for 82% of whole metals, and all the other metals are in described oily product.For industrial operation, the formation of bottoms stream is minimized, because on behalf of the synthetic crude product, it reduce 18%, and produce the more product logistics of low value, this can influence described method aspect economy and the processing.
Make not diluted Boscan crude oil reaction with supercritical water process of the present invention before, measure its character.The character of described crude oil is as follows: at 60/60 time api gravity is that 9,40 ℃ of following viscosity are 1140CST; The C/H ratio of 8.0wt%; The MCRT of 16wt%; The sulphur of 5.8wt%; The vanadium of 1280ppm.Described not diluted Boscan crude oil is converted into synthetic crude after supercritical water treatment, this synthetic crude has following character: at 60/60 time api gravity is that 22,40 ℃ of following viscosity are 9CST; The C/H ratio of 7.6wt%; The MCRT of 2.5wt%; 4.6% sulphur; Vanadium with 130ppm.
Contrast initial crude oil and simulation distil analysis, show that synthetic crude prepared in accordance with the present invention obviously has the character more superior than initial crude oil from the synthetic crude product of different experiments operation.Especially, described synthetic crude contains the more low boiler cut of high score rate.51% diluted Hamaca crude oil seethes with excitement in less than 1000 temperature range, and use is according to the method for use supercritical water of the present invention, configuration according to method, seethe with excitement at the synthetic crude between 79% to 94% less than 1000 temperature range, 40% not diluted Boscan crude oil seethes with excitement in less than 1000 temperature range, and using method according to use supercritical water of the present invention, 93% synthetic crude seethes with excitement in less than 1000 temperature range.
According to instruction described herein and supportive embodiment, might carry out many variations to the present invention.Therefore be understandable that, in following claim scope, can by remove this paper institute specially the mode description or the illustration put into practice the present invention.
Claims (19)
1. hydrocarbon is carried out the method for upgrading, comprise
(a) hydrocarbon is heated to the fluid that temperature is higher than the water of its critical temperature and mixes in the mixing zone to form mixture with comprising;
(b) described mixture is passed to reaction zone;
(c) described mixture is not reacted in described reaction zone under condition of supercritical water outside having under the situation of hydrogenation, the residence time is enough to allow the upgrading reaction to take place;
(d) take out the homogeneous reaction product from described reaction zone; And
(e) described reaction product is divided into the hydrocarbon phase of gas phase, effluent water and upgrading.
2. according to the process of claim 1 wherein that described hydrocarbon is to be selected from full cut heavy crude crude oil, tar sand bitumen, the acquisition heavy hydrocarbon from heavy hydrocarbon fractions, heavy vacuum gas oil, vacuum residuum, petroleum tar, coal tar and their mixture of petroleum crude oil.
3. according to the process of claim 1 wherein that the aqueous fluid of described bag enters described mixing zone under the temperature of the critical temperature that fully is higher than water, so that resulting mixture has the temperature higher than the critical temperature of water.
4. according to the method for claim 3, the aqueous fluidic temperature of wherein said bag is 400-600 ℃.
5. according to the process of claim 1 wherein that the described hydrocarbon temperature in the step (a) is 100 ℃～200 ℃.
6. according to the process of claim 1 wherein that described condition of supercritical water comprises that temperature is 374 ℃～1000 ℃, pressure is 3205psia～10000psia, and oil/water volume ratio is that 1: 0.1～1: 5 and the wherein said residence time are 1 minute～6 hours.
7. according to the process of claim 1 wherein that described condition of supercritical water comprises that temperature is 374 ℃～600 ℃, pressure is 3205psia～7200psia, and oil/water volume ratio is that 1: 0.5～1: 3 and the wherein said residence time are 8 minutes～2 hours.
8. according to the process of claim 1 wherein that described condition of supercritical water comprises that temperature is 374 ℃～400 ℃, pressure is 3205psia～4000psia, and oil/water volume ratio is that 1: 1～1: 2 and the wherein said residence time are 20～40 minutes.
Under the situation of catalyzer that provides in no any outside according to the mixture that the process of claim 1 wherein in the described reaction zone or promotor in reaction.
10. according to the method for claim 1, also be included in the middle described mixture that forms of step (a) is passed to the step that described reaction zone is higher than described mixture heating up to temperature the supercritical temperature of water before.
11. hydrocarbon is carried out the method for upgrading, comprising:
(a) with hydrocarbon with comprise the fluid of water that temperature is higher than the critical temperature of water and in the mixing zone, mix the mixture that is higher than the critical temperature of water with formation temperature;
(b) described mixture is passed to reaction zone;
(c) described mixture is reacted in described reaction zone under condition of supercritical water under the situation of not having outer hydrogenation and catalyzer, the residence time is enough to allow upgrading reaction generation;
(d) take out the homogeneous reaction product from described reaction zone; And
(e) described reaction product is divided into the hydrocarbon phase of gas phase, effluent water and upgrading.
12. according to the method for claim 11, wherein said hydrocarbon is to be selected from full cut heavy crude crude oil, tar sand bitumen, the acquisition heavy hydrocarbon from heavy hydrocarbon fractions, heavy vacuum gas oil, vacuum residuum, petroleum tar, coal tar and their mixture of petroleum crude oil.
13. according to the method for claim 11, the aqueous fluid of wherein said bag is fully entering described mixing zone under the temperature greater than the critical temperature of water, so that resulting mixture has the temperature higher than the critical temperature of water.
14. according to the method for claim 13, the aqueous fluidic temperature of wherein said bag is 400-600 ℃.
15. according to the method for claim 11, wherein the described heavy hydrocarbon temperature in the step (a) is 100 ℃～200 ℃.
16. according to the method for claim 10, wherein said condition of supercritical water comprises that temperature is 374 ℃～1000 ℃, pressure is 3205psia～10000psia, and oil/water volume ratio is that 1: 0.1～1: 5 and the wherein said residence time are 1 minute～6 hours.
17. according to the method for claim 10, wherein said condition of supercritical water comprises that temperature is 374 ℃～600 ℃, pressure is 3205psia～7200psia, and oil/water volume ratio is that 1: 0.5～1: 3 and the wherein said residence time are 8 minutes～2 hours.
18. according to the method for claim 10, wherein said condition of supercritical water comprises that temperature is 374 ℃～400 ℃, pressure is 3205psia～4000psia, and oil/water volume ratio is that 1: 1～1: 2 and the wherein said residence time are 20～40 minutes.
19., also be included in the middle described mixture that forms of step (a) passed to the step that described reaction zone is higher than described mixture heating up to temperature the critical temperature of water before according to the method for claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/555,130 | 2006-10-31 | ||
| US11/555,130 US20080099377A1 (en) | 2006-10-31 | 2006-10-31 | Process for upgrading heavy hydrocarbon oils |
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| Publication Number | Publication Date |
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| CN101553553A true CN101553553A (en) | 2009-10-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2007800403123A Pending CN101553553A (en) | 2006-10-31 | 2007-10-30 | Process for upgrading heavy hydrocarbon oils |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20080099377A1 (en) |
| CN (1) | CN101553553A (en) |
| CA (1) | CA2666673A1 (en) |
| EA (1) | EA200970438A1 (en) |
| WO (1) | WO2008055162A2 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CA2666673A1 (en) | 2008-05-08 |
| WO2008055162A2 (en) | 2008-05-08 |
| EA200970438A1 (en) | 2009-10-30 |
| US20080099377A1 (en) | 2008-05-01 |
| WO2008055162A3 (en) | 2008-07-10 |
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