CN103534338A - Method for the continuous obtention of synthesis gas from oil sand and/or oil shale - Google Patents

Method for the continuous obtention of synthesis gas from oil sand and/or oil shale Download PDF

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Publication number
CN103534338A
CN103534338A CN201280020210.6A CN201280020210A CN103534338A CN 103534338 A CN103534338 A CN 103534338A CN 201280020210 A CN201280020210 A CN 201280020210A CN 103534338 A CN103534338 A CN 103534338A
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oil
process chamber
sand
vertical process
gas
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T·斯图浦
U·伯肯多夫
L·保曼
R·穆勒
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Ecoloop GmbH
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Ecoloop GmbH
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/06—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/06—Continuous processes
    • C10J3/12—Continuous processes using solid heat-carriers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

The invention relates to a method for the continuous obtention of synthesis gas by the direct gasification of carbon fractions contained in oil sands and/or oil shales in a vertical process chamber (2) having a calcination zone and an oxidation zone (6), in which the calcinated, fractions rich in carbon oxidize with oxygen-containing gas. The gaseous reaction products are withdrawn at the top of the vertical processing chamber (2) that has the shape of a vertical shaft furnace which is continuously flown through from the top to the bottom by a bulk material which itself is not oxidized. Oxygen-containing gas (10) is at least partially introduced beneath the oxidation zone, whereby the rising gas flow is facilitated. The bulk material is at least partially provided by the natural inert rock content in the oil sands and/or the oil shales. Added alkaline substances convert under reductive conditions the gaseous sulfur compounds, which were obtained at temperatures above 400 DEG C from the constituents of the oil sands and/or the oil shales, by chemical reaction into solid sulfur compounds which are at least partially discharged with the gaseous reaction products and are removed from the gas phase at temperatures above 300 DEG C by fine material separation (18).

Description

From oil-sand and/or resinous shale, obtain continuously the method for synthetic gas
The present invention relates to by thering is the vertical process chamber of calcining zone and oxidation zone, the carbon component that direct gasification contains in oil-sand and/or resinous shale obtains the method for synthetic gas continuously, in oxidation zone, with oxygen-containing gas, be oxidized the rich carbonaceous component through calcining, wherein at top, vertical process chamber, extract gaseous reaction products, and vertical process chamber is vertical pit furnace form, unoxidized bulk materials itself from it by the continuous flow of top to bottom, wherein oxygen-containing gas is introduced under oxidation zone at least in part, promote thus upstream, wherein the natural inertia rock constituents by oil-sand and/or resinous shale provides bulk materials at least in part, by under reductive condition, add alkaline matter by vertical process chamber in the temperature higher than 400 ℃ from oil-sand and/or the gaseous sulfur compound that obtains of resinous shale component, by carrying out chemical reaction with described alkaline matter, be converted into solid-state sulphur compound, it is discharged with gaseous reaction products at least partly, and from gas phase, removing by thin separating substances higher than 300 ℃ of temperature.
Because whole world tight demand fossil oil and the raw material based on oil, and the long-term lacking as expected of traditional oil, from resinous shale and/or oil-sand resource recovered energy carrier and raw material, become day by day important.
The asphalt mixture that natural oil-sand or resinous shale comprise natural rock and contain as many as 20%.This asphalt mixture mainly contains the Organic Compounds of different molecular weight and boiling point.
Background of invention
In order to realize the specific aim of these carbon compounds, reclaim, must be first that asphalt mixture is separated with natural rock component.
Pitch can mainly complete by two kinds of technology from the separation of these natural rock mass.
Surface mining is obtained:
In the method, the rock mass that contains pitch is abolished with load-carrying dredger or wheel loader, and be transported to processing plant with load transportation instrument.In general, process and complete with following process steps:
1. fragmentation/porphyrize rock is generally supplied with water vapour or hot water simultaneously
2. produced suspension is delivered to the first extraction step, wherein precipitation and water form bottom separating layer, and pitch and foam shape thing formation top separating layer.
3. common, bottom precipitation and water layer are delivered to artificial lake or watery diarrhea lake.
4. upper brea bed is delivered to the second extraction step, wherein water and fine particle resistates are separated.Conventionally, pitch is dissolved in to organic solvent (being generally " petroleum naphtha ", is the product of light oil acquisition process).Obtain so-called crude asphalt.
5. crude asphalt is delivered to bituminous treatment (" upgrading ") subsequently.
Obtaining of so-called " in-situ method ":
In this technology, from soil, under top layer and do not obtain crude asphalt fragmented rock body.This technology realizes as follows:
6. by high-pressure steam injection as dark bituminous rock stratum.Realize thus the hydrothermal solution of crude asphalt.
7. this liquefaction crude asphalt is delivered to underground bleeding point pointedly, and by suitable pumping technology, be pumped to earth's surface from it.
8. the crude asphalt usually, so obtaining carries out the corresponding program of above-mentioned steps 5.
From crude asphalt, extract light oil and liquid fuel:
In subsequent disposal factory (" upgrading "), merge crude asphalt (may from two kinds of preparation methods).Wherein conventionally carry out following process steps:
9. from comprising the mixture of crude asphalt and petroleum naphtha, steam except volatile hydrocarbon.Finally remaining is insoluble resistates, is called petroleum coke.Depend on material used, it can contain the sulphur component of as many as 10%.
10. by fractional condensation, the hydrocarbon gas from distillation is separated into petroleum naphtha, kerosene and gas oil; Generally petroleum naphtha is back in process at least in part.
11. depend on the quality of independent fraction needs, and devulcanization can complete in all the other steps.This conventionally removes elementary sulfur by hydrogenation separation and completes.
The terminal of 12. processes is to preserve and transport liquid fraction.
Yet, for thering is remarkable economy and environment shortcoming from the aforesaid method of resinous shale and/or oil-sand acquisition light oil and fuel.
For example, from rock mass, extract the hot water and steam that crude asphalt needs appreciable amount.For every volume element light oil, must use the water of as many as 6 volume elements.The preparation of steam and hot water completes conventionally in the boiler of gas-firing.High and cause extremely disadvantageous energy balance in whole process to the demand of Sweet natural gas.In addition every barrel of the acquisition specific CO that light oil is corresponding, 2quantity discharged take into account environmental problem and in view of valuable scarce resource be substantially unacceptable.
Although strive at least part of cycling use of water, the high water consumption of aforesaid method causes corresponding pollutant effluents high rate.Because said process, waste water not only contains precipitation and also mainly contains the pitch of residual concentration, also referred to as the polynuclear aromatic compound of PAK, and heavy metal.PAK is the mixture of the aromatics organic substance of various molecular weight.In PAK mixture, toxicant generally accounts for the overwhelming majority.Especially, must mention and suspect carcinogenic benzopyrene.
These pollutant effluents are deposited in artificial lake or artificial lagoon conventionally.They cause the extremely high risk pollution to nature and environment therein.This its, partly affect maximum in the world artificial water.
The sulphur that contains concentration as many as 10% at distillation crude asphalt (step 9) remaining petroleum coke afterwards.This is valuable energy carrier substantially.Yet because high sulfur content, it can not be easily for combustion processes, such as producing water vapour or hot water.Therefore, guarantee that eco-friendly thermal utilization is problematic, even if may be only also that to take that out-of-proportion flue gas desulfurization (FGD) changes into be originally cost.
Therefore, the object of this invention is to provide the method for the various shortcomings without prior art, but it allows the carbon support that on environment, utilization suitable and Energy Efficient contains in oil-sand and/or resinous shale, and do not cause a large amount of pollution resistatess.Meanwhile, also provide and save the method for utilizing fossil oil (such as Sweet natural gas), himself can produce enough energy carriers to supply with the necessary energy requirement that utilizes process.
According to the present invention, by obtaining the synthetic gas of low-sulfur, solve the problems referred to above: by thering is the vertical process chamber of calcining zone and oxidation zone, the carbon component that direct gasification contains in oil-sand and/or resinous shale, in oxidation zone, with oxygen-containing gas, be oxidized the rich carbonaceous component through calcining, wherein at top, vertical process chamber, extract gaseous reaction products, and vertical process chamber is vertical pit furnace form, unoxidized bulk materials itself from it by the continuous flow of top to bottom, wherein oxygen-containing gas is introduced under oxidation zone at least in part, promote thus upstream, wherein the natural inertia rock constituents by oil-sand and/or resinous shale provides bulk materials at least in part, by under reductive condition, add alkaline matter by vertical process chamber in the temperature higher than 400 ℃ from oil-sand and/or the gaseous sulfur compound that obtains of resinous shale component, by carrying out chemical reaction with described alkaline matter, be converted into solid-state sulphur compound, described solid-state sulphur compound is discharged with gaseous reaction products at least partly, and from gas phase, removing by thin separating substances (18) higher than 300 ℃ of temperature.
In order can especially effectively to gasify, be included in the carbon component in oil-sand or resinous shale, advantageously before they enter vertical process chamber by mechanical energy by oil-sand or resinous shale porphyrize to the particle size that is less than 300mm.As a result of, in vertical process chamber, react and can especially effectively carry out, reason is that in this situation, the reaction table area of oil-sand or resinous shale is increased, and has guaranteed gas permeability enough in bulk materials simultaneously.
The another preferred implementation of the inventive method is, as alkaline matter, uses metal oxide, metal carbonate, the mixture of 2 kinds or 3 kinds in metal hydroxides or these materials.They can be metered in the gas phase of top, Zhong Huo calcining zone, vertical process chamber pointedly.Another possibility be before entering vertical process chamber by metal oxide, metal carbonate, in metal hydroxides or these materials, the mixture of 2 kinds or 3 kinds mixes with oil-sand and/or resinous shale.
Confirmed particularly advantageously, the fine particulate form that is less than 2mm with particle size is used alkaline matter at least in part, as solid matter and/or aqeous suspension.
Metal oxide used, metal carbonate and metal hydroxides contain alkali metal and alkali earth metal and particularly preferably contain calcium confirmed it is particularly preferred as cationic modification.Calcium has advantage herein, and corresponding substance oxidation calcium used, calcium carbonate or calcium hydroxide have suitable physics and chemistry material behavior, to obtain in the methods of the invention the almost result of the best about the combination of gaseous sulfur compound.The sulphur compound of the calcium producing in addition, be particularly suitable for surpass the temperature of 300 ℃ from gas phase as solid separation remove.
The method of prior art also usually has significant technical problem so far, and reason is the formation of the split product that contains oil or tar.In the methods of the invention, these problems are solved, wherein, in vertical process chamber and/or in the gas phase of the gaseous reaction products of discharging, under water vapour and calcium oxide and/or calcium carbonate and/or calcium hydroxide existence, in the temperature higher than 400 ℃, carry out calcium catalytic reforming.During the course, the essential component with the split product that is greater than C4 chain length producing that contains oil and/or tar is converted into carbon monoxide, carbonic acid gas and hydrogen.
Necessary water vapour can be metered in the gas phase of top, in vertical process chamber and/or calcining zone pointedly.A kind of embodiment is also favourable, wherein from the residual water-content original position of oil-sand and/or resinous shale, provides water vapour.In this case, can need not be metered into water completely and carry out.
In principle, the inventive method also can be carried out abreast with above-mentioned each method of prior art for the separated crude asphalt of rock constituents from oil-sand or resinous shale.In this case, the moisture medium that utilizes process for example to extract from crude asphalt from oil-sand, can also advantageously be used for calcium catalytic reforming as water.
In order to ensure the especially effectively form of the inventive method, advantageously via gas phase, from vertical process chamber, remove a high proportion of as far as possible fine particle alkaline matter and solid-state sulphur compound.Said process is realized like this: the flow velocity of the gaseous reaction products extracting in top, vertical process chamber is reached at least 10m/s by suitable process control, thereby guarantee at least in part to remove fine particle alkaline matter and solid-state sulphur compound from vertical process chamber through gas phase.
For the success of the inventive method, importantly provide during the course sufficient alkaline matter with combined sulfur product.Shown that fine particle alkaline matter must be with 1g/Nm at least 3the metering of the gaseous reaction products producing is than using, to obtain good result.Thus, also guarantee that total dust concentration in the gas phase of the gaseous reaction products of discharging is for 1g solid/Nm at least 3.This minimum dust concentration has proved that to guarantee to produce low-sulfur synthetic gas stabilization process necessary.
For effectively that dust is separated from synthetic gas, advantageously fine particle alkaline matter and solid-state sulphur compound carry out via static filter surface from the thin separating substances of gas phase, at it, to flowing solid-state filtrate plasma membrane in side, form dark filtering layer.Through this, guaranteed the final close contact of gaseous state split product and fine particle alkaline matter before final thin separating substances, to make gaseous sulfur compound and the alkali substance reaction of maximum and remove from system.
The required bulk materials moving-bed of method forms by the rock constituents of oil-sand used or resinous shale at least partly.Yet, depend on the characteristic of oil-sand or resinous shale, can advantageously by being additionally metered into thick material, supplement bulk materials moving-bed, to increase mobility and/or and the gas permeability of bulk materials.Advantageously, thick material mixed with oil-sand or resinous shale before entering vertical process chamber.
Found that method can particularly advantageously operate if the mixture of the mineral substance of particle size 2mm to 300mm and/or other inorganic substance or each material is used as to thick material.If the timber of particle size 2mm to 300mm and/or other biogenic material are used as to thick material, realize same good result.
The important adjustable parameter of method operation is the metered amount of oxygen-containing gas and the total λ producing.Under reductibility summer condition, carry out process, wherein at this, the total λ by whole stages of process chamber is adjusted to and is less than 0.5.Preferably, method can also be with 0.3 or total λ operation still less.
The asphalt content that depends on oil-sand used or resinous shale, can be suitable be by adding extra carbon support to increase heat production value.It is completed advantageously, before entering vertical process chamber, carbon support is mixed with oil-sand or resinous shale.
In order to ensure flowing as far as possible uniformly of bulk materials process vertical process chamber, oxygen-containing gas can be delivered to vertical process chamber with pressure pulse form.Consequent mechanical force contributes to flowing of loose and/or reinforcement bulk materials.These pressure pulses can for example trigger with regular intervals of time, thereby in bulk materials, form bridging or obstruction in initial just prevention.
The advantage that the inventive method has is that the crude asphalt being contained in oil-sand/resinous shale no longer needs with separation method heavy on complexity, environment separated from rock substance; On the contrary, in single method step, it can be converted into high value synthetic gas especially effectively with on environment acceptably, and it mainly comprises carbon monoxide, hydrogen and lower hydrocarbon.Special advantage is, the synthetic gas purity that obtains is like this very high and sulphur content is low, and so can be for many other processes.For example, may synthetic gas be converted into various hydrocarbon by adopting Fischer-Tropsch to synthesize, or liquid fuel.The favourable reason of this embodiment height is: because untapped, go out the inventive method, will produce and precipitate and waste water, or will produce petroleum coke in crude asphalt separation; In contrast, the inventive method can realize whole organic constituents of oil-sand/resinous shale to the conversion completely of synthetic gas.
Fig. 1 shows a kind of exemplary embodiment of the inventive method.The inventive method is explained in its expectation, but does not limit its scope.
The oil-sand that surface mining obtains or resinous shale (A) are via crusher system (1) mechanical disintegration to being less than the particle size of 30cm and being delivered to adverse current gasifier (2) from top via vertical chute, and it consists of vertical process chamber.Bulk materials forms by the rock constituents from oil-sand/resinous shale (A) wholly or in part.The quality and the physical properties that depend on oil-sand or resinous shale, can advantageously sneak into bulk materials by the thick material (3) of more particle size 2mm to 300mm.In the time need to improving the flow behavior of bulk materials or gas permeability, this is suitable especially.
Other carbon support (4) can be sneaked into bulk materials to increase the ratio of the utilized carbon in bulk materials.Except timber and biogenic material, can also use many various carbon supports.For example, or even the resistates producing in oil-sand or resinous shale utilization.Especially, this can be bitumeniferous throw out or petroleum coke.
The mixture of bulk materials, thick material and resistates by gravity by the vertical process chamber (2) of flowing through, top to bottom.Adverse current gasifier has the burner gun (5) of central region, and it guarantees the steady progression of the burning of given tensile load in vertical process chamber and calcination district (6).These burner guns energy enough fossil oils (7) and oxygen-containing gas (8) operate.As the standby ground of selecting of fossil oil, can also use the synthetic gas from adverse current gasifier (9).
In lower end, vertical process chamber, introduce oxygen-containing gas (10).This gas first, before bulk materials leaves vertical process chamber, it is cooling in cooling zone (11).Thereby oxygen-containing gas obtains preheating along with continuing upwards to flow in vertical process chamber.According to adverse current gasification principle, from the oxygen of oxygen-containing gas and the carbonaceous material generation oxidizing reaction in bulk materials, and regulate the amount of oxygen-containing gas to make to regulate the total λ in vertical process chamber to be less than 0.5.Thus, form the first calcination district (6), wherein the resistates of carbonaceous material reacts to form CO with oxygen 2.In process chamber, upwards more oxygen minimizing is more, thereby finally only carbonization at low temperature can occur, until upwards farther, all oxygen finally exhausts, and under reductive condition, is forming cracking zone (12) completely.
On the contrary, if from observed the logistics of the bulk materials mixture that comprises oil-sand/resinous shale, bulk materials and alkaline matter by top to bottom, what in cracking zone (12), first occur is the dry of general moistening material used, until reach the internal temperature of 100 ℃.After this, the internal temperature of material further raises, and causes gasification to start, and starts to form methane, hydrogen and CO when 500 ℃ of internal temperature as many as.After extensive degassed, the internal temperature of material is because hot gas rises and further rises from calcination district (6), completely degassed thereby final carbonaceous material is able to, and only comprises residual coke, so-called cracking coke, and grey component.Cracking coke and bulk materials be transportation further downwards in vertical process chamber, wherein its higher than 800 ℃ of temperature with from the CO in calcination district 2component is converted into CO by Boudouard transform portion, and gasification similarly.Some in cracking coke also this region be present in equally the water vapour generation water-gas reaction in hot gas, form CO and hydrogen.Finally, in the temperature ， calcination district (6) lower than 1800 ℃, the oxygen-containing gas that the resistates of cracking coke retinue below flows into is after-flame and be able to thermal utilization virtually completely.Thus, the adverse current gasifier supply of institute's energy requirement that may obtain in fact all gasifying.This is also referred to as self-heating gasification.
As extra cooling and gasification medium, water (13) can also be metered into cooling zone via water spray gun (14).
The synthetic gas forming in vertical process chamber extracts by suction (15) in upper end, thereby in upper gas chamber (16), adjusts the slight low pressure of 0 to 200 millibar.
The quality that depends on material used can produce the gaseous sulfur compound of significant quantity during gasification.Therefore advantageously, if oil-sand/resinous shale and bulk materials are sneaked into alkaline matter (16) before entering vertical process chamber.For this intention, metal oxide, metal hydroxides or metal carbonate are suitable especially, and it is particularly preferred using fine particle calcium oxide, reason is it because reactive and high surface area spontaneously react and also form thus solid-state sulphur compound with the gaseous sulfur compound forming, and it removes by suction mainly together with the synthetic gas of vertical process chamber and extraction.Other pollutent such as chlorine, hydrogenchloride or even heavy metal can highly effectively be combined with CaO and from process, remove in the same manner.
Extraly, can be suitable be to use coarse particles metal oxide, metal hydroxides or metal carbonate as bulk materials (3), on the one hand so as to increase bulk materials and carbonaceous material ratio and on the other hand to also make also can obtain in the bottom of vertical process chamber alkali reaction companion with in conjunction with gaseous sulfur compound.
The synthetic gas extracting by suction contains dust, and it mainly comprises solid-state sulphur compound, fine particle alkaline matter, other pollutent, and inert particle.This synthetic gas that contains dust can be processed in the gas compartment (16) of vertical process chamber; Or after being that (15) leave vertical process chamber, under water vapour and the existence of fine particle calcium oxide, higher than the temperature of 400 ℃, processed.This temperature can regulate the amount of oxygen-containing gas (10) to be regulated by the lower end in vertical process chamber aptly, or the heat production of the burner gun (14) by calcination district output is regulated.Yet, particularly advantageously, via with fuel and oxygen-containing gas or even excessive oxygen-containing gas stoichiometry the burner gun (17) that operates, use the direct burning in synthetic gas.The oil that this hot aftertreatment under water vapour and calcium oxide existence still exists in guaranteeing synthetic gas and tar are by the katalysis cracking of calcium oxide.
Then, containing dust synthetic gas, in the temperature higher than 300 ℃, pass through hot gas filtration (18) shedding dirt.The Chalk-dust filtering of sulfur-bearing (19) leaches from process, and discarded or for the standby purposes of selecting.In the preferred implementation of the inventive method, also Chalk-dust filtering again as fine particle alkaline matter, may be mixed with bulk materials in (16) at least partly, with part circulation pattern, operate thus.
The synthetic gas producing (9) is sulfur-bearing not in fact, and can be as raw material and the fuel in different application.
The needs that depend on other application of place conditioned disjunction synthetic gas, can be essential be utilize can complete before with gas cooler (20) cooling syngas and remove condensation product.The condensation product (21) producing can be used as cooling and gasification medium via water spray gun (14) again at least in part in vertical process chamber.
The bulk materials mixture (22) that vertical reaction chamber lower end produces mainly contains coarse particles bulk materials, grey resistates, and fine particle bulk materials.Fine particle bulk materials can also contain a small amount of sulphur product and other pollutent.
Whole logistics in bulk can wholely store (23).Yet, particularly preferably be screening bulk materials mixture (24), wherein can preferably thick fraction (25) be introduced at least in part to circulation and again be used as the bulk materials of vertical process chamber in (3).
The fraction of carefully sieving (26), removes from process with together with the Chalk-dust filtering (19) of sulfur-bearing, discards or for the standby purposes of selecting.Again, in the preferred implementation of the inventive method, the fraction of carefully sieving may be mixed at least in part again at least part of cyclical operation of the fraction that promotes thus carefully to sieve with bulk materials in (16) as fine particle alkaline matter.

Claims (18)

1. by the carbon component that in the vertical process chamber (2) having calcining zone (12) and oxidation zone (6), direct gasification contains in oil-sand and/or resinous shale, obtain continuously the method for synthetic gas, in described oxidation zone, with oxygen-containing gas (10), be oxidized the component that is rich in carbon through calcining, wherein at top, vertical process chamber (15), extract gaseous reaction products, described vertical process chamber forms vertical pit furnace form, unoxidized bulk materials itself from its continuously by top to flows, oxygen-containing gas is introduced under oxidation zone at least partly, promote whereby upstream, it is characterized in that, bulk materials provides by the natural inertia rock constituents of oil-sand and/or resinous shale at least partly, by under reductive condition, add alkaline matter (16) by vertical process chamber in the temperature higher than 400 ℃ from oil-sand and/or the gaseous sulfur compound that obtains of resinous shale component, by carrying out chemical reaction with described alkaline matter, be converted into solid-state sulphur compound, this solid-state sulphur compound is discharged with gaseous reaction products at least partly, and from gas phase, removing by thin separating substances (18) higher than 300 ℃ of temperature.
2. the method for claim 1, is characterized in that, by mechanical energy, oil-sand and/or resinous shale is crushed to the particle size that is less than 300mm before entering vertical process chamber (2).
3. the method for one of aforementioned claim, it is characterized in that, as alkaline matter, use metal oxide, metal carbonate, the mixture of 2 kinds or 3 kinds in metal hydroxides or these materials, and be metered into pointedly vertical process chamber (2) and/or add the gas phase of calcining zone (12) top, and/or mix with oil-sand and/or resinous shale before entering vertical process chamber (2).
4. the method for claim 3, is characterized in that, described metal oxide, and metal carbonate, and the metal hydroxides element that contains alkali-metal element or alkaline-earth metal, particularly preferably contain calcium as positively charged ion.
5. the method for one of aforementioned claim, it is characterized in that, in vertical process chamber (2) and/or in the gas phase of the gaseous reaction products of discharging, under water vapour and calcium oxide and/or calcium carbonate and/or calcium hydroxide existence, in the temperature higher than 400 ℃, carry out produced having and be greater than the calcium catalytic reforming of the oil-containing of chain length of C4 and/or the important component of the split product of tar, be translated into carbon monoxide, carbonic acid gas and hydrogen.
6. the method for claim 5, is characterized in that, water vapour is metered into pointedly vertical process chamber (2) and/or adds the gas phase of top, calcining zone (12), and/or provides from the residual water-content original position of oil-sand and/or resinous shale.
7. the method for one of aforementioned claim, is characterized in that, the fine particulate form that described alkaline matter is less than 2mm with particle size is at least partly as solid matter and/or as aqeous suspension.
8. the method for one of aforementioned claim, is characterized in that, will utilize process from oil-sand, and for example the moisture medium from crude asphalt extraction is used as water.
9. the method for one of aforementioned claim, it is characterized in that, the flow velocity of the gaseous reaction products extracting in top, vertical process chamber (2) reaches at least 10m/s by suitable process control, thereby guarantees at least in part to remove fine particle alkaline matter and solid-state sulphur compound from vertical process chamber through gas phase.
10. the method for one of aforementioned claim, is characterized in that, described fine particle alkaline matter is with 1g/Nm at least 3the metering of gaseous reaction products to be generated is than using, and through this, guarantees that total dust concentration in the gas phase of the gaseous reaction products of discharging is for 1g solid/Nm at least 3.
The method of one of 11. aforementioned claims, it is characterized in that, fine particle alkaline matter and solid-state sulphur compound carry out via static filter surface from the thin separating substances (18) of gas phase, at it, to flowing solid-state filtrate plasma membrane in side, form dark filtering layer, through this, guarantee the final close contact of gaseous state split product and fine particle alkaline matter before final thin separating substances, to make gaseous sulfur compound and the alkali substance reaction of maximum.
The method of one of 12. aforementioned claims, it is characterized in that, bulk materials moving-bed partly adds thick material by extra metering and forms, to increase mobility and/or its gas permeability of bulk materials, wherein said thick material mixed with oil-sand and/or resinous shale before entering vertical process chamber.
The method of 13. claims 12, is characterized in that, uses thick material, mineral substance and/or other inorganic substance or the substance mixture of the particle size with 2mm to 300mm.
14. claims 12 or 13 method, is characterized in that, uses timber and/or other biogenic material of the particle size with 2mm to 300mm as thick material.
The method of one of 15. aforementioned claims, is characterized in that, is less than 0.5 and preferably 0.3 or the reductibility summer condition of total λ still less through whole stages of process chamber.
The method of one of 16. aforementioned claims, is characterized in that, before entering vertical process chamber, extra carbon support is mixed with oil-sand and/or resinous shale, to increase the concentration that can utilize carbonaceous component in bulk materials moving-bed.
The method of one of 17. aforementioned claims, is characterized in that, with pressure pulse form, oxygen-containing gas is delivered to vertical process chamber, to promote flowing of loose and/or reinforcement bulk materials by these mechanical forces.
The method of one of 18. aforementioned claims, is characterized in that, the synthetic gas of generation is at least in part as producing hydrocarbon such as the synthetic raw material of the Fischer-Tropsch of fuel.
CN201280020210.6A 2011-03-18 2012-03-16 Method for the continuous obtention of synthesis gas from oil sand and/or oil shale Pending CN103534338A (en)

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