CN86104452A - Method for partical oxidation - Google Patents
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- CN86104452A CN86104452A CN86104452.5A CN86104452A CN86104452A CN 86104452 A CN86104452 A CN 86104452A CN 86104452 A CN86104452 A CN 86104452A CN 86104452 A CN86104452 A CN 86104452A
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- 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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
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Abstract
The refinery coke of partial oxidation sulfur-bearing and nickeliferous, vanadium and silicon ash content and/or heavy liquid hydrocarbon material are produced synthetic gas.Iron-containing additive enters reaction zone with raw material.Additive A is used for the raw material of low silicon content, combines with part of nickel component and sulphur, produces a kind of flushed in liquid phase agent.Also can contain the additional materials that is selected from nickel, chromium and its mixture on a small quantity in the additive, be dispersed in the refinery coke, molten state residue viscosity is low, is easy to discharge from separator, and prolong the work-ing life of refractory liner.Additive B is used for the raw material of high silicon content, and (i) part produces the flushed in liquid phase agent, and (ii) part produces a kind of liquid-phase oxidation thing-silicate.
Description
The present invention relates to heavy liquid hydrocarbon fuel oil, the refinery coke that contains ash content or their mixture that partial oxidation contains ash content produces and contains H
2The gaseous mixture of+CO.More particularly, the present invention relates to a kind of additive system, be used to remove the ash content that the pollutent of the nickeliferous and vanadium that produces when the refinery coke of the heavy liquid hydrocarbon fuel oil of and vanadium ash nickeliferous at partial oxidation, nickeliferous and vanadium ash or their mixture are produced synthetic gas, reducing gas or fuel gas and other have melted.
Partial oxidation liquid hydrocarbon fuel oil as the fuel of petroleum products and hydrocarbon solid, is known method as the slurries of coal and refinery coke.The foreseeable trend of prospective oil is that petroleum is more and more heavier, degradation.In order to compensate this trend, petroleum refiner must use more residua upgrading so that needed light-end products to be provided.The present industrial means that this upgrading is provided are coking (delayed coking or fluid coking) of some hydro carbons.Now a large amount of refinery enlargings comprise newly-built or the enlarging coker, and therefore, coking will become the method that generally adopts in some times in future.
Making the principal element of coking method stagnation is product Jiao's processing.With the coking raw material of normal degree of cleaning, its product coke has been substituted the almost application of pure carbon material, as the electrode manufacturing.Yet along with charge raw material oil quality variation, some just having occurred influences the composite factor of coker running.At first, because stock oil contains more pollutent, i.e. sulphur, metal (mainly being vanadium, nickel, iron) and ash content, these pollutents concentrate among product Jiao, these burnt poor quality and can not satisfy normal product requirement.Secondly, because stock oil becomes heavy, that is to say that containing more Jiao expects composition, what cinder coal was produced from every barrel of heavy liquid hydrocarbon fuel oil that contains ash content like this is just many.Produce particle refinery coke existing description in No. 3673080 patents of the U.S. with delayed coking process.The fluid coking method has description in No. 2709676 patents of the U.S..
Texaco (Texeaco) partial oxidation gasification process provides the processing coke or has contained the alternately operational path of the heavy liquid hydrocarbon fuel oil of ash content.For example, the slurries of refinery coke and water react with No. 3607157 of the U.S. partial oxidation process that patent provided.Gasification is often as the means that make things convenient for of handling coke.Fu Laikexi pyrogenic process (Flexicoking Process) is the binding operation of coker and gasification installation, but owing to the design of gasification installation has been subjected to criticism.And, do not produce fusing refinery coke ash content with the reduction of ash content temperature of fusion.Gasification as this conclusion of means of handling coke based on economic benefit.Give the phase energy expenditure rising and require all to utilize the rules of stock oil will cause utilizing in a large number the charging of refinery coke very soon as partial oxidation gas generator.
Be that some unexpected operational issues appearred in the gasifying process of raw material with delay coke and the heavy-fluid body hydrocarbon fuel oil that contains ash content in the past.Be generally molten state and do not melt fully and discharge as the ash content that residue is drained from gasifier, the result is deposited on the wall of refractory masses.Vanadium and nickel component are collected on the gasifier wall and in the downtime and form oxide compound in the above-mentioned ash content.The gasifier wall is exposed to after the atmosphere, and these settlings that contain vanadium will be on fire, and vanadium then becomes the V of eutectic
2O
5Or vanadium metal hydrochlorate.Its strong solvency action of the oxide compound of the vanadium on the refractory masses can cause the obstruction of gasifier outlet at bottom.Nickel impurity forms very disagreeable nickle carbonoxide settling in the system rear portion under certain conditions.All do not provide the method that solves vanadium and nickel problem in coal gasification and the dilution process that in No. 1799885 patents of the U.S. and No. 2644745 patents, uses.One of purpose of the present invention is that the on-stream time of prolongation oxidation gasification installation and the district's refractory masses that can not induce reaction because of the existence owing to vanadium damage and to stop work.
It is raw material is produced the gaseous mixture of H+CO with partial oxidation method with the heavy liquid hydrocarbon fuel oil that contains nickel and vanadium ash or with the refinery coke or the mixture of the two that contain nickel and vanadium ash that first aspect of the present invention provides a kind of; Above-mentioned raw materials contains minimum for 0.5%(weight) sulphur; Contain in the above-mentioned ash and minimumly be that 0.5%(is heavy) vanadium and minimumly be the 2.0%(weight) nickel, also contain silicon; Above-mentioned method is characteristics with the following step:
(1) when the content of silicon in the above-mentioned ash during less than about 350ppm, mix iron-containing additive A in the stock oil, when the silicone content in the above-mentioned ash is about 400ppm or when being higher than 400ppm, mix iron content and calcium additive B in the raw material, wherein additive A or B in the reaction zone described in (2) with the ratio of ash branch greatly within 1.0-10.0 is than 1.0 scope, when using additive A, the vanadium of each part needs 10 parts iron at least, when using additive B, (vanadium of each part) needs 10 parts of iron+calcium at least;
(2) in the temperature range of 1200 ℃-1650 ℃ (2200-3000), in about 5-250 atmospheric pressure range, refractory-lined unrestricted flow is being arranged, the partial oxidation reaction district, (1) mixture of said raw material and additive is under the situation that has temperature alleviant to exist in, with the gas reaction that contains free oxygen, output is by H under reducing environment
2The fusion residue that the hot-fluid that+CO forms goes out air-flow and carries secretly; When using additive A, at reaction zone, at least a portion nickel component in above-mentioned additive and the raw material and sulphur combine and form irrigation mutually, and this irrigation to major general's part contains the oxide compound bar of vanadium, and spinel and other ash component and the broken end of refractory materials put together and take out of reaction zone; When using additive B, (I) part of the additive of said iron content and calcium combines with the part of said nickel, calcium and sulphur and generates the liquid phase irrigation, the oxide compound bar that a part can be contained vanadium, spinel, the broken end of other ash content and refractory materials puts together and takes away, (II) combines with said nickel, calcium and silicon and produces liquid oxidation thing-silicic acid salt face, and this liquid oxidation thing-silicate can wash away all remaining barium oxide bar and spinel and other ash component of containing basically
(3) from the eluting gas of heat, separate non-gaseous phase substance.
Second aspect of the present invention provide a kind of with the heavy liquid hydrocarbon fuel oil that contains nickel and vanadium ash content or with the refinery coke that contains nickel and vanadium ash content or the mixture of the two be raw material with partial oxidation production by H
2The method of the gaseous mixture that+CO forms, above-mentioned raw materials is minimum, and to contain 5.0%(heavy) vanadium, it is minimum that to contain 2.0%(heavy) nickel, also contain silicon; Described method comprises:
(1) when the content of silicon in the above-mentioned ash content during approximately less than 350ppm, stock oil mixes iron-containing additive A, when the content of silicon in the above-mentioned ash content is approximately 400ppm or is higher than 400ppm, and the additive B of admixture iron content and calcium in the stock oil; Wherein additive A or additive B in the reaction zone described in (2) with the ratio of ash greatly about 1.0-10.0 than 1.0 scope in, when using additive A, the vanadium of each part needs 10 parts iron at least, and when using additive B, (vanadium of each part) needs 10 parts of iron+calcium at least;
(2) stock oil in the coking (1) and the mixture of additive are produced refinery coke, and this refinery coke contains nickel and vanadium ash content and contains scattered additive A or B;
(3) with refinery coke of producing in (2) with pumpable refinery coke-aqueous slurry state, liquid hydrocarbon fluids or their mixture are delivered to the partial oxidation reaction district, or the drystone oil coke form of carrying secretly with the gas delivery medium substantially is admitted to reaction zone;
(4) in the temperature range of 1200 ℃-1650 ℃ (2200-3000), in about 5-250 barometric pressure range, refractory-lined unrestricted flow partial oxidation reaction district is being arranged, (3) refinery coke described in generates by H with the gas reaction that contains free oxygen having under slow mixture existence of temperature and the reducing environment
2The hot-fluid that+CO forms goes out air-flow and the residue of the fusing of carrying secretly; When using additive A, at reaction zone, said iron-containing additive at least with raw material in a part of nickel component and sulphur in conjunction with forming the flushed in liquid phase agent, this irrigation at least can part contain the oxide compound bar of vanadium, spinel, the broken end of other ash component and refractory materials is collected and is taken reaction zone out of; When using additive B, said iron content, calcium additive (I) part combine with said part of nickel, calcium, sulphur and form the flushed in liquid phase agent, this irrigation can be with part contain the barium oxide bar, spinel, other ash content and refractory materials are collected and are taken away, the nickel of (II) and said part, calcium and silicon are in conjunction with Generation Liquid oxide body-silicic acid salt face, and basically with the remaining oxide compound bar that contains vanadium, spinel and other ash component all wash away;
(5) go out to separate non-gaseous phase substance the air-flow from said hot-fluid.
With compound form,, send the supplementary additive that is selected from magnesium, chromium or their mixtures on a small quantity to reaction zone as oxide compound.Magnesium and chromium can further prolong the refractory-lined life-span.
The partial oxidation of heavy liquid hydrocarbon fuel oil and refinery coke is described in No. 4411670 patents of the U.S. and No. 3607156 patents respectively.Moreover, aforesaid reference paper has also been described refractory liner free flow pattern producer gas generator and the nozzles that are applicable to these raw material production synthetic gas, reducing gas and fuel gas.Method advantage of the present invention is to use inexpensive relatively raw material, comprises heavy liquid hydrocarbons raw oil and/or refinery coke nickeliferous, the vanadium ash content.It is heavy that above-mentioned raw materials contains minimum 0.5%() sulphur, for example 2.0%(is heavy at least) sulphur, above-mentioned ash content is minimum, and to contain 5.0%(heavy) vanadium and minimum 2.0%(heavy) nickel, for example 2.0～5.0%(is heavy) and some silicon.
By definition, the heavy liquid hydrocarbons or the fuel that contain nickel and vanadium ash content are meant that making oil or the coal chosen oil, shale oil, tar sand oil or their mixtures from various crude oil, crude distillation and cracked residual oil, fraction oil of petroleum, tops, whole crude oil, pitch, coal tar, coal makes fuel.
By definition, the refinery coke that contains nickel and vanadium ash content is meant that with the heavy liquid hydrocarbon fuel that contains ash content be the coking method of raw material with routine, such as the refinery coke that delayed coking or fluid coking method are produced, above-mentioned two kinds of coking methods have narration in No. 3673080 patents of the U.S..
Under the situation that does not add additive, the resulting ash content of forming with the heavy liquid hydrocarbon fuel oil and/or the refinery coke of the ash content that contains nickel and vanadium of raw material partial oxidation be studies show that more at large they mainly are made up of the oxide compound of vanadium, nickel, iron and sulfide and the inorganic substance that exist with mineral forms usually.Also exist by vanadium, vanadium+calcium, vanadium+iron, vanadium+aluminium, and their mixture form contain the barium oxide bar, and the spinel type aluminic acid salt face of forming by this group material of vanadium, iron, chromium, aluminium, magnesium and their mixture contain vanadic spinel.A large amount of interior existence that connect pin are the high reasons of residue viscosity on the stripe shape xln.
The metal that is present in the ash content provides a system, and it is different from the metal system in the coal greatly.Important factor is that the total ash content of refinery coke and heavy liquid hydrocarbon fuel oil is 0.5～5%(weight), and the typical number of ash content of coal content is 10～20%(weight).Relative low ash oontent may be just to remove the reason that ash problems is just noted after gasification installation comes into operation for a long time in refinery coke and heavy liquid hydrocarbon fuel oil.Ash content that works and additive blended chance significantly reduce, and these additives are with vanadium component flushing and to take reaction zone out of necessary.
Confirm that theoretically a large amount of ashy substances in heavy liquid hydrocarbons and refinery coke are released to the individual molecule form.This is because there be (being only limited to the atoms metal of inorganic structure, oxide compound or ion) in the metal in the crude oil with the porphyrin-type structure, and through distillation and cracking, these metallic forms in the crude oil just are sandwiched in the carbon structure that has collapsed.
When heavy metal components was piled up in system, problem had just been come.Particularly, known under normal gasification condition, vanadium and nickel are piled up on the reaction zone refractory lining backing of partial oxidation gas generator, and are not to flow out from gasifier equably.In the downtime, these storess that comprise vanadium just can be on fire after being exposed in the air, vanadium is converted into the V of eutectic
2O
5With vanadium metal hydrochlorate state.Verified, these materials are very strong to the corrodibility of refractory materials, therefore, reduced gasifier reaction zone refractory-lined work-ing life.Use the method that we study, the problems referred to above and other problems can minimize, because in the method for our research, can significantly reduce or be eliminated in the quantity of the remaining vanadium component of reaction zone.
The present invention includes a kind of application of iron-containing additive.More particularly, work in-process is when the raw material silicon content that contains ash content during less than about 350ppm, we recommend to use above-mentioned additive A ', when the raw material silicon content that contains ash content is approximately 400ppm or is higher than 400ppm, recommend to use above-mentioned additive B.But also provide a kind of these additives (being called additives) that in system, add to obtain the method for maximum efficiency.
Describe the working method of using the low raw material of additive A machine silicon content below in detail.
Iron-containing additive A contains a kind of iron cpd, preferably ferric oxide.Reaction zone at the partial oxidation gasifier, at least a portion in additive and the raw material, as being whole or most of substantially, promptly about 40～100%(is heavy), for example about 70-90%(weight) nickel component and sulfuration are closed, and form low viscous flushed in liquid phase agent or carry agent.Its advantage is, the cost that potential sulphur content and posterior means remove sulphur in the gas in the gas of production can reduce significantly maybe and may eliminate.This irrigation is to be in liquid phase under the temperature of reaction zone, and its composition is that the about 75-95%(of iron sulphide is heavy), such as approximately 80-90%(is heavy), about 0.5～the 3%(of nickelous sulfide is heavy), heavy such as 1-2%(), the about 2-9%(of ferric oxide is heavy), heavy such as 3-6%().The viscosity of this irrigation when 1093 ℃ (2000) is at about 10-20 pool (Poises).And be surprised to find that this flushed in liquid phase agent contains the barium oxide bar and spinel has very strong wetting capacity to high temperature is immobilising.The effect of this irrigation is different fully with the dilution additive that is used for dissolving the coal residue.Such as, this irrigation does not dissolve bothersome barium oxide bar and the spinel of containing.But they are flushed out reaction zone as carrying agent.This irrigation will contain at least a portion of pollution of vanadium thing, and will be heavy as about 40-100%(), be generally about 60-80%(and weigh), whole pollution of vanadium things develop from the reaction zone of gasifier under the better situation.The mixture of this flushed in liquid phase agent and barium oxide belongs to residue, and it is heavy that it approximately contains 1～10%(), as the barium oxide of about 4-8%.And then, be surprised to find that silicone content will disturb greater than 350ppm to form this flushed in liquid phase agent in the partial oxidation reaction district.
Also be surprised to find that, if in iron additive, comprise from element magnesium, chromium family and their mixture in the auxiliary substance selected can obtain other benefit.These elements provide with the suitable compound form, and this compound is selected from oxide compound, oxyhydroxide, carbonate, supercarbonate, vitriol and nitrate and their mixture.1.0～10.0%(that magnesium in additive, the compound of chromium and their amount of the mixture can be additive is heavy), heavy such as 20～80%().The magnesium and/or the chromium cpd that add above-mentioned additives amount can make the residue component of fusing refractory materials saturated, stop them to continue dissolving from refractory materials.Therefore the refractory-lined life-span obtains prolonging.
One of the iron-containing additive of proper amt and raw material enter reaction zone, satisfy following two ratios: (I) at the part by weight of reaction zone iron-containing additive and ash content (non-combustible materials) greatly in 1.0～10.0 to 1 scope, generally be at least 2: 1, for example the weight ash content of each part will add the iron-containing additive of 5 parts weight in the raw material charging; The vanadium of (II) each part weight is wanted 10 parts of weight at least, and general about 10-30 is preferably the iron of 20 parts of weight.
The advantage of method of the present invention is, compares with the high viscosity residue of prior art, and the residue that generates at reaction zone has lower viscosity, promptly moors less than 20 when 1093 ℃ (2000 °F).This is easy to the removing of residue.Thereby when gasification installation was stopped work, reaction zone refractory liner inwall was clean, the accumulation of no pollution of vanadium thing.
Under reducing environment, partial oxidation reaction carries out under following condition: temperature is (from 2200 °F to 3000 °F) from 1200 ℃ to 1650 ℃, be generally about 1260～1480 ℃ (about 2300 °F～2700 °F), for example, approximately 1500-1550 ℃ (about 2725 °F-2825 °F); Pressure:, be generally about 15 to 200 normal atmosphere from about 5 to 250 normal atmosphere; When with water vapor or water during as temperature alleviant, the part by weight of water/fuel should be in about 0.1 to 5.0 scope, as 0.2 to 0.9; The atomic ratio of carbon in free oxygen and the fuel (0/c than) should be about 0.6 to 1.6, such as 0.8 to 1.4.
It is probably as follows that the hot-fluid that directly leaves unrestricted flow partial oxidation gasifier reaction zone goes out the composition of air-flow, represents with Mo Er percentage ratio: H
2: 10 to 70; CO:15 to 57; CO
2: 0.1 to 25; H
2O:0.1 to 20; CH
4: 0 to 60; H
2S:0 to 2; COS:0 to 0.1; N
2: 0 to 60; Ar:0 to 2.0.Granular carbon is heavy about 0.2-20%(greatly) in the scope (carbon is radix in charging).Ash amount is about 0.5 to 5.0%(heavy), as 1.0-3.0%(based on the raw material gross weight).Product gas can be used as synthetic gas, reducing gas or fuel gas, this will be according to removing the granulated carbon of bringing gas into chilling and/or WATER-WASHING METHOD, dehydration or do not dewater after gas composition and decide.
Iron-containing additive is except that being used to produce irrigation, and as previously mentioned, it also has unexpected catalytic property.For example, its effect can be more from coking process production and/or the light-end products of better quality.In gasification reaction, thereby it also can increase the throughput of gasification installation by increasing speed of response, or the transformation efficiency of raising cigarette ash improves the total efficiency of this method.Yet the present invention does not rely on the catalytic property of iron-containing additive.
Also be surprised to find that, the heavy liquid hydrocarbon fuel oil or the nickeliferous and reasonable iron-containing additive of the refinery coke blended vanadium ash content that are used for nickeliferous and vanadium ash content comprise from oxide compound, vitriol, carbonate, prussiate, muriate, the iron cpd of choosing in the nitrate and their mixture.As iron cpd, water-soluble molysite is useful.This iron cpd can be from naphthenate, oxalate, acetate, Citrate trianion, a kind of ferrous mineral compound of choosing in benzoic acid salt, oleate, tartrate and their mixtures or ferric iron mineral compound.Additive A is very thin fine powder, and it is by ground.
In the single job of methods described herein, contain fuel mixture and one of the iron-containing additive that refinery coke nickeliferous and vanadium is formed in the heavy liquid hydrocarbon fuel oil of nickel and vanadium and/or the ash content in the above-mentioned ash content and send the partial oxidation gasifier to.In another time operation, the heavy liquid hydrocarbon fuels that contains nickel and vanadium in this iron-containing additive and the ash content mixes, and mixture is sent the coker production refinery coke of routine to then.In this way, the iron-containing additive that is fine powder is blended in the refinery coke product fully.The comparatively good particle size of ground iron-containing additive and ground refinery coke is in about 210-37 micrometer range of ASTM E-11 standard sieve regulation or littler.Each component of said mixture can be worn into fine powder respectively and mix then.On the other hand, also dry powder grinding or wet-milling grind each component together.The granular size of each solid matter of mixture should be done equally substantially, reaches the mixing fully of this solid matter thus.Powder mixture can the two mixes with water or liquid hydrocarbon material or with it, and making solids content is that 50-65%(is heavy) the slurry carried of available pump, this solid matter also can carry out wet-milling with slurry medium.On the other hand, the mixture of granular solids also can be mixed in the gas phase media, is delivered into gasifier then.The gas-phase transport medium can be from water vapor, CO
2, N
2, contain in gas phase, circulation synthetic gas and their mixture of free oxygen and choose.
In the operation of aforesaid way, the iron-containing additive that is fine powder mixes with heavy liquid hydrocarbon fuel oil nickeliferous and vanadium in the ash content, and be sent to coking tower, additive also can directly be added vacuum still and contain in the petroleum liquid charging of ash, and the subsequent processing of vacuum still is exactly coking usually.In the operation of any device (coking or distillation), all basically iron-containing additives should be present in the residual oil logistics of hope.In other words, should be seldom with the additive that is pulled away than light product, if any.Additive is sneaked into the vacuum distillation tower charging, is that the viscosity of viscosity ratio vacuum residuum of vacuum distillation tower charging is little than being mixed in the possible benefit of vacuum residuum (coking charging).Can mix more fully.
For example, a kind of high boiling liquid petroleum, be nickeliferous and the heavy liquid hydrocarbon fuel of vanadium ash content and the mixture of iron-containing additive, in about 340 ℃-500 ℃ (about 650-930) temperature ranges, send the delayed coking reaction district to, for example the method for being narrated by No. 3673080 patents of the U.S. 33 row.In 430 ℃ of-480 ℃ of temperature ranges and 3.30-9.93 crust (approximately 20-60 pound/inch) pressure range, incoagulable vapour phase hydrocarbon effluent and water vapor leave from the top, and the refinery coke that is mixed with iron-containing additive goes out clearly from bottom, pyrogenic reaction district.
In another operating method, a kind of high boiling liquid oil and ferruginous additive agent mixture of nickeliferous and vanadium ash content, send the fluidized carbonization reaction zone in about 290-400 ℃ of (about 550-750) temperature range, for example the method for being narrated by No. 2709676 patents of the U.S. 31 row.Cling in the pressure range of (approximately 10-20 pound/inch) at temperature range and about 1.65-3.30 of about 540 ℃-650 ℃ (about 1000-1200), incoagulable hydro carbons flows out vapour and water vapor leaves from the top, and coke is come out clearly from the pyrogenic reaction district.
In the operation of another kind of mode, method of the present invention can be used for other similar petroleum technology process, is gasification installation production proper raw material.Any " residual oil " treatment process all can not make residual oil or residua upgrading, and reaches the most degree of pricking of eating up, and finally must produce some logistics like this.These logistics or liquid, or be solid under standard state, but under the lifting temperature, can use pump delivery, they all cause the gasification problem, as the coke of discussing.Therefore, introduce the part of iron-containing additive as the refining of petroleum method before the gasification, this notion should be able to be produced the raw material that does not have above-mentioned gasification problem according to specific processing method.Most of such complete processings underpressure distillation as giving treating processes.Accordingly, as mentioned above, iron-containing additive can be with nickeliferous, and the underpressure distillation charging of vanadium ash content mixes mutually.This additive will leave distillation tower, appear at the bottom of the tower in the oil.Oil itself is exactly the charging of modification process at the bottom of this tower.Mixing of this iron-containing additive do not have the opposite effect to these technological processs, and this additive finally will appear at the richness of each technological process with in the bottoms stream that contains vanadium.In these all processing methodes, this bottoms stream should be the suitable feedstock of partial oxidation gasifying process.
During the applied research of additive A, be surprised to find that, with a kind of calcium cpd and the raw material of narrating in the past, it is the oil charcoal, liquid hydrocarbon fuel oil or the mixture of the two mix mutually, the softening temperature of additive can reduce about 56-167 ℃ (approximately 100-300 °F), as about 111 ℃ (about 200 °F).This calcium cpd optional autoxidation calcium, lime carbonate and calcium hydroxide.By adding calcium, the partial oxidation gasifier can go into operation under lower temperature, promptly approximately reduces by 111 ℃-167 ℃ (approximately 200-300 °F).When going into operation, calcium cpd can lean on and charging and/or iron-containing additive blended method, temporarily sends the partial oxidation reaction district to, and the decisive amount that calcium cpd is sneaked into approximately is that the 2-8%(of additive A weight is heavy) or lower.Calcified material can reduce the softening temperature of additive, thereby increases the rate of recovery of sulphur in the residue.Find that also the 8%(that calcium cpd surpasses additive A is heavy) time, sulfurated lime and lime carbonate will block the centre channel of soaking tub, thereby have stopped up and left the discharge that reaction zone leads to the hot effluent air-flow of quench tower.
Soon, when sulphur began to shift in the residue of fusing, the liquid curing slag of iron and nickel will reduce the softening temperature of iron-containing additive after going into operation, and had therefore cancelled the necessity of later adding calcium.Excessive calcium can reclaim sulphur, and forms the heavy-gravity sulfide phase of non-hope.Make calcium contents remain on iron-containing additive 8.0% or low, will guarantee the flushing of dystectic sulfurated lime phase and dystectic vanadium bar and spinel.In this method, use calcium by mixing with iron-containing additive, be different from No. 4277365 patents narrate calcium is used as flux widely.
Following example I can make people understand relevant treatment process of hanging down the silicon raw material among the present invention better, but the present invention is not limited.
The embodiment I
There is the partial oxidation reaction district of refractory liner to produce mainly in unrestricted flow and contains (in mole %) H
2: 25-45, CO:20-50, CO
2: 5-35, CH
4: 0.06-8.0 and CO
2+ H
2The synthetic gas of S:0.1-2.0 is as described in No. 3607157, United States Patent (USP).Raw material is formed by a kind of drystone oil coke spray water xi solution disperse phase of nickeliferous and vanadium ash content or by the drystone oil coke disperse phase of the ash content that is entrained in the nickeliferous and vanadium in the gas phase transmission medium that the gas that contains free oxygen and water vapor mixture form.Ash content contains and is about 12.0%(weight in the refinery coke) vanadium, about 5.0%(weight) nickel and the silicon that is less than about 250ppm.About 3.2%(weight) sulphur is present in the refinery coke.The nickel and the vanadium that are contained in the ash content are arranged in the refinery coke, be evenly distributed on about 100% in the refinery coke in addition and be the iron-containing additive of ferric oxide.Iron-containing additive is about 5 to 1 to the weight ratio of ash content.At reaction zone iron the weight ratio of vanadium is about 16 to 1.In another operation, nickeliferous and the refinery coke of vanadium and the additive blending of iron content and calcium in the ash content, with the defeated slurry of the available pump of a kind of refinery coke in water, input unrestricted flow partial oxidation reaction district.Solids content in the slurries is about 60%(weight).
In the temperature buffer agent, as H
2O, CO
2, N
2Exist down, in refractory-lined partial oxidation reaction district, under about 1510 ℃ high temperature and about 6 normal atmosphere, refinery coke and gas react as the free oxygen in air, oxygen-rich air, the pure oxygen.The fusion cinder drips grain because gravity or because chilling and/or wash with the air-flow of being with water or other purge of gas media and to be easy to make it to separate from the hot gas flow that leaves reaction zone.The melt temperature of liquid ceanser and ash content is below 1150 ℃.As a comparison, the melt temperature of the thick residue ash content of iron-containing additive then is not higher than 1510 ℃.The chemical constitution of residue sees Table 1.
The chemical constitution of table 1 residue
The residue type
And source FeS NiS FeO CaO CaS SiO
2V
2O
3Other
(1)
Liquid phase 81.1 1.2 4.1 0.8 1.2 1.1 6.3 4.2
Irrigation
(1) a small amount of ash content and refractory materials regenerant powder.
Accompanying drawing 1 is the section shape photo (amplifying 500 times) of the residue produced by the flushed in liquid phase agent, shows undissolvedly to contain barium oxide bar L and spinel S is in the matrix of liquid phase clean-out system M.
Be similar to the employing additive A mentioned the front in the technological operation of low silicon raw material than the technological operation of the raw material of high silicon content, adopt additive B in raw material than high silicon content.To further narrate the use of additive B below.
Than the raw material of high silicon content be those silicone contents greater than 350ppm, promptly about 400ppm and the raw material that is higher than 400ppm, for example about 400ppm to about 5000ppm, particularly scope at 450ppm between the 1000ppm.
Use the additive B of iron content and calcium unexpected effect to be arranged mutually to producing two kinds of residues, i.e. a flushing phase of having said for the front mutually, another is the oxide/silicate phase of fused raw material ash content mutually.Therefore, additive B works with dual mode.
As mentioned above, high silicon content can hinder additive A to generate liquid phase irrigation phase.Yet use additive B, be surprised to find that this obstruction of high silicon content no longer exists.
The additive of iron content and calcium contains 30.0-90.0%(weight), for example about 50.0-80.0%(weight) iron cpd, ferric oxide preferably, remaining is calcium cpd, preferably calcium oxide substantially.For example, the 10-70%(weight of can having an appointment in iron-calcium additive), be generally about 20-50%(weight) calcium oxide.In the reaction zone of partial oxidation gas generator, the major portion of additive, 10-90%(weight for example), generally be 25-75%(weight) with raw material in major part, for example about 40-95%(weight), general about 70-90%(weight) nickel component and sulphur combine, and produce low viscous flushed in liquid phase agent or carrier.With above-mentioned additive A, the cleaning charge of advantageously potential sulphur in gas and discharge air-flow reduces greatly even can exempt.The same with additive A, this irrigation is liquid phase under temperature of reaction, and the about 75-95% of Containing Sulfur iron is generally 80-90% substantially, and the about 0.5-3% of nickelous sulfide is generally 1-2%, and the about 2-9% of ferric oxide is generally 3-6%.This clean-out system is in the viscosity under the 1093 ℃ also scope at 10-20 pool.
This irrigation washs out about 20-80%(weight of partial oxidation gas generator), be generally 60-70%(weight) contain the pollution of vanadium thing.Use iron content-calcium additive to be different from United States Patent (USP) 4277365 said lime carbonate fusing agent in essence by this way to produce irrigation.
The remainder of iron content and calcium additive unexpectedly with at least a portion that in reaction zone, stays, for example about 30-100%(weight), be generally 50-80%(weight) nickel, calcium and silication close, produce liquid oxidation thing-silicic acid salt face, basic dissolving all contains barium oxide bar and spinel and other ash contents, produces a kind of uniform substantially slag.Usually, sila matter and high-melting-point foreign matter of vanadium are immiscible, therefore be can not fusion they.Yet, the invention solves this problem.Liquid oxidation thing-silicic acid salt face has following chemical constitution (by weight): the about 10-70% of calcium oxide, be generally 20-50%, the about 0-1.0% of sulfurated lime is generally 0.01-0.50%, the about 5-25% of silicon-dioxide, be generally 1-10%, the about 0-0.5% of nickelous sulfide is generally 0.01-0.05%, and a small amount of ash content and the about 2-10% of refractory materials regenerant, be generally 3-6%.Contain the 1-10%(weight of having an appointment with the residue that liquid oxidation thing-silicate generates mutually), be generally the vanadium oxide of 3-7%.
The same with additive A, it is useful adding a kind of above-mentioned said additional substances in the additive of iron content and calcium, and these annexation are selected from magnesium, chromium, manganese element and composition thereof.These elements provide with suitable compound, select from oxide compound, oxyhydroxide, carbonate, supercarbonate, vitriol, nitrate and composition thereof.The total amount of magnesium, chromium, manganese or their mixture can be in the 1.0-10.0%(of additive weight in additive) in the scope, be generally 2.0-8.0%(weight).
The magnesium and/or the chromium cpd that add above-mentioned auxiliary quantity come saturated residue to prevent these component corrosion refractory materialss.Therefore the life-span of refractory masses obtains prolonging.Also be surprised to find that and add the flowability that manganic compound can increase residue.Particularly, add manganic compound, for example manganese oxide causes reducing the melt temperature of ash content and improves the flowability that contains the oxide compound-silicate residue that dissolves vanadium.
Join the additive A that the quantity of the iron content of reaction zone and calcium additive B can have been narrated with reference to the front with fuel feedstocks.
The advantage of additive B of the present invention is to produce two types slag at reaction zone, and each all has low viscosity, and viscosity is lower than 20 pools in the time of 1093 ℃, as the molten slag of existing processing method relatively higher viscosity is arranged then.Help the removing of residue like this.And when gasifier stopped, the refractory wall of reaction zone cleaned, and did not have the accumulation of pollution of vanadium thing basically.
Partial oxidation reaction occurs under the reduction reaction environment, except temperature preferably is no more than 1593 ℃, and can be with reference to the condition of above-mentioned additive A.
For additive B, iron and calcium cpd are that the compound of the iron preferably that adopted with above-mentioned additive A is identical preferably.
The following examples II provides better explanation to the processing treatment about the raw material of high silicon content among the present invention, but the present invention is not limited.
The embodiment II
There is the partial oxidation reaction district of fire-resistant support lining to produce mainly in unrestricted flow and contains (mole %) H
2: 25-45, CO:20-50, CO
2: 5-35, CH
4: 0.06-8.0, and CO
2+ H
2The synthetic gas of S:0.1-2.0.As described in No. 3607157, United States Patent (USP).Raw material is formed by a kind of refinery coke aqueous solution disperse phase of vaporific nickeliferous and vanadium ash content or by the drystone oil coke disperse phase of the ash content that contains nickel and vanadium in the gas delivery medium that is entrained in the gas that contains free oxygen and steam mixture.It is heavy that ash content in the refinery coke contains 12%() vanadium, 5.0%(weight) nickel and the silicon of 650ppm.Also have 1.8%(weight in the refinery coke) sulphur.Nickeliferous and vanadium ash content is arranged in the refinery coke, and contain the homodisperse iron content therein and the additive agent mixture of calcium, its additive contains 75%(weight) FeO and 25%(weight) CaO.The additive of iron content and calcium is about 5 to 1 with the weight ratio of ash branch.Iron calcium in the reaction zone is about 25 to 1 with the weight ratio of vanadium.In another time experiment, the refinery coke that contains nickel, vanadium ash content is sent into unrestricted flow partial oxidation district with the mixture of iron content, calcium additive with the refinery coke of available pump conveying and the slurry form of water.Solids content in this slurry oil is about 60%(weight).
Refinery coke is at partial oxidation district that is lined with refractory liner and the gas that contains free oxygen, for example: air, oxygen-rich air, pure oxygen, and at temperature alleviant, as H
2O, CO
2, N
2Existence under react, its melt temperature is 1510 ℃ (about 2750 °F), pressure is about 6 normal atmosphere.The way that the residue particles of fusing can be easily washed by gravity or chilling or water and other gaseous media goes out the air-flow to separate from the hot-fluid that leaves reaction zone.From the temperature of fusion of the ash content of oxide compound-residue that the silicate fluid generates mutually-℃ (°F) as follows: initial set temperature 1249(2280) °, softening temperature 1282(2340), yield temperature 1316(2400).Residue is under the condition of 1357 ℃ (2475), and viscosity is 15 pools.The fluid temperature (F.T.) of liquid wash agent and mixing ash content is lower than 1149 ℃ (2100 °F).Comparatively speaking, the ash content temperature of fusion in the thick residue of iron-free calcium additive is higher than 1510 ℃ (2750 °F).The chemical composition of the residue of two kinds of forms sees Table II.
The composition of two kinds of dregs of fat of table II
The residue type
And source FeS NiS FeO CaO CaS SiO
2V
2O
3Other
(1)
A: liquid phase 81.1 1.2 4.1 0.8 1.2 1.1 6.3 4.2
Irrigation
B: oxygen 9.8 0.01 34.2 31.7 0.9 13.1 5.9 5.3
Change thing-silicate
(1) Wei Liang ash content and refractory materials powder.
Photomicrograph shown in Figure 1 is the representative section figure of the A type residue that produces with the flushed in liquid phase agent, with above-mentioned example I make similar.
See Fig. 2 by the liquid oxidation thing-silicic acid salt face and the sectional view Photomicrograph (amplifying 500 times) of the Type B residue of the component generation that contains lysed vanadium.
Claims (10)
1, partial oxidation contains the heavy liquid hydrocarbon fuel raw material of nickel, vanadium ash content, or contain the refinery coke raw material of nickel, vanadium ash content, or its mixture, production contains the processing method of the gaseous mixture of H+CO, the sulphur that contains at least 0.5% (weight) in the above-mentioned raw materials, the vanadium that contains at least 5.0% (weight) in the above-mentioned ash content, the nickel of at least 2.0% (weight) and some silicon; Described processing method is characterised in that the following step:
(1) described raw material and iron content (when the silicone content in the described ash content during less than 350ppm) additive A is mixed mutually, or mix with iron content, calcium (silicone content in its ash content be about 400ppm or more for a long time) additive B, wherein additive A or B in the reaction zone described in (2) with the weight ratio of ash branch within 1.0-10.0 is than 1.0 scope, if employing additive A, the vanadium of per 1 part of weight needs the iron of 10 parts of weight at least, perhaps, if the employing additive B, the vanadium of then per 1 part of weight needs at least 10 parts of iron+calcium.
(2) the unrestricted flow reaction zone of refractory liner is being arranged, temperature range is that 1200 ℃ 1650 ℃ (2200-3000) pressure are 5-250 normal atmosphere, (1) described mixture is having under slow mixture existence of temperature and the reducing environment, with the gas reaction that contains free oxygen, the fusing residue of producing the feed gas stream of the heat that contains H+CO and carrying secretly, in described reaction zone, when adopting additive A, at least a portion nickel component in described iron-containing additive and the raw material and sulphur generation combination reaction, produce a kind of flushed in liquid phase agent, at least a portion is contained the oxide compound bar of vanadium to this irrigation and reaction zone is collected and taken out of to the component of spinel and other ash content and refractory materials; When adopting additive B, described iron content, calcium additive (I) part combine with the described nickel of part, calcium and sulphur, produce a kind of flushed in liquid phase agent, the component that part is contained barium oxide bar and spinel and other ash content and refractory materials gathers up and takes out of reaction zone, (II) part becomes a kind of liquid oxidation thing-silicic acid salt face with described nickel, calcium and silication symphysis, can be almost all described barium oxide bar, spinel and other ash content of containing of remainders fuse.
(3) the non-pneumatic material is separated from described hot charge gas stream.
2, partial oxidation contains the heavy liquid hydrocarbon fuel raw material of nickel, vanadium ash content, or contain the refinery coke raw material of nickel, vanadium ash content, or its mixture, production contains the processing method of the gaseous mixture of H+CO, contain 0.5%(weight at least in the described raw material) sulphur, at least contain 5.0%(weight in the described ash content) vanadium, 2.0%(weight) nickel, also contain some silicon; Described processing method comprises:
(1) described raw material and iron content (when the silicone content in the described ash content during less than 350ppm) additive A is mixed mutually, or mix with iron content, calcium (silicone content in its ash content be about 400ppm or more for a long time) additive B, wherein additive A or B in the reaction zone described in (2) with the weight ratio of ash branch within 1.0-10.0 is than 1.0 scope, if employing additive A, the vanadium of per 1 part of weight needs the iron of 10 parts of weight at least, perhaps, if employing additive B, the vanadium of then per 1 part of weight need 10 parts of iron+calcium at least;
(2) coking (a 1) described mixture generates the refinery coke that contains nickel, vanadium ash content and dispersive additive A or B;
(3) refinery coke that (2) are prepared, with the refinery coke aqueous slurry that a kind of available pump is carried, liquid hydrocarbon fluids or its mixture, or, be incorporated into the partial oxidation reaction district with the form that the gas transmission medium is carried the drystone oil coke secretly;
(4) the partial oxidation reaction district of refractory liner is arranged in described unrestricted flow, temperature range is that 1200 ℃-1650 ℃ (2200-3000) pressure are 5-250 normal atmosphere, (3) described refinery coke is having under slow mixture existence of temperature and the reducing environment, with the gas reaction that contains free oxygen, produce outflow logistics that contains the H+CO hot charge and the residue of carrying secretly, in described reaction zone, when adopting additive A, at least part of nickel component and reaction of Salmon-Saxl in described iron-containing additive and the raw material, produce a kind of flushed in liquid phase agent, near small part contains the barium oxide bar, and reaction zone is collected and taken out of to the component of spinel and other ash content and refractory materials; When adopting additive B, described iron content, calcium additive (I) part combine with the described nickel of part, calcium and sulphur, produce a kind of flushed in liquid phase agent, part is contained the barium oxide bar, the component of spinel and other ash content and refractory materials gathers up and takes out of reaction zone, (II) part becomes a kind of liquid oxidation thing-silicic acid salt face with the described nickel of part, calcium and silication symphysis, incite somebody to action almost all remaining barium oxide bars that contain, spinel and the fusion of other ash content;
(5) the non-pneumatic material is separated from described hot charge gas stream.
3, according to the processing method of claim 1 or 2, comprise described additive A or B are added the step in the oil at the bottom of the charging of vacuum distillation apparatus or the tower, carry out described mixing.
4,, be included in and sneak into enough additive A or this process of B in the step (1), so that the whole sulphur in the raw material change into the sulfide of iron and nickel, so that make described sulphur leave reaction zone with residue according to claim 1 or 2 described processing methodes.
5, according to the method for claim 1 or 2 described use additive A, comprise that step (a) is that 2.0%～8.0% calcium cpd of described iron-containing additive A weight joins the reaction zone of partial oxidation reactor to reduce the softening temperature of iron-containing additive when going into operation with quantity, (b) go into operation after, stop to carry out step (a).
6,, comprise by in additive A or B, adding the step that magnesium and/or chromium make improvements according to claim 1 or 2 described processing methodes.
7, according to claim 1 or 2 described processing methodes, wherein said flushed in liquid phase agent contains following weight % component, iron sulphide 75-95, nickelous sulfide 0.5-3.0, ferric oxide 2-9.
8, according to claim 1 or 2 described processing methodes, wherein additive B contains 30.0%-90.0%(weight) iron cpd, remainder is calcium cpd basically.
9,, be included in the additive B and add in magnesium, chromium and the manganese that total amount is the 1.0-10.0% of weight of additive at least a metal pair it carries out the step of upgrading according to claim 1 or 2 described processing methodes.
10,, wherein when using additive B, contain manganese oxide in the additive B according to claim 1 or 2 described processing methodes.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/749,375 US4668428A (en) | 1985-06-27 | 1985-06-27 | Partial oxidation process |
| US749375 | 1985-06-27 | ||
| US06/749,376 US4668429A (en) | 1985-06-27 | 1985-06-27 | Partial oxidation process |
| US749376 | 1991-08-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86104452A true CN86104452A (en) | 1987-04-29 |
| CN1007262B CN1007262B (en) | 1990-03-21 |
Family
ID=27115109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86104452A Expired CN1007262B (en) | 1985-06-27 | 1986-06-26 | Method of partial oxidation |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPH0772081B2 (en) |
| KR (1) | KR940005198B1 (en) |
| CN (1) | CN1007262B (en) |
| AU (1) | AU586260B2 (en) |
| DE (1) | DE3667180D1 (en) |
| ES (1) | ES8801165A1 (en) |
| IN (1) | IN165846B (en) |
| MX (1) | MX168358B (en) |
| PT (1) | PT82831B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102245747A (en) * | 2008-12-08 | 2011-11-16 | 通用电气公司 | Gasifier additives for improving refractory life |
| WO2013159270A1 (en) * | 2012-04-23 | 2013-10-31 | General Electric Company | Partial oxidation feed system and method |
| CN103391989A (en) * | 2011-02-23 | 2013-11-13 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock with nickel recovery |
| CN103814118A (en) * | 2011-07-27 | 2014-05-21 | 沙特阿拉伯石油公司 | Process for the gasification of heavy residual oil with particulate coke from delayed coking unit |
| CN104302574A (en) * | 2012-03-27 | 2015-01-21 | 沙特阿拉伯石油公司 | Integrated process for the gasification of whole crude oil in a membrane wall gasifier and power generation |
| US9702372B2 (en) | 2013-12-11 | 2017-07-11 | General Electric Company | System and method for continuous solids slurry depressurization |
| US9784121B2 (en) | 2013-12-11 | 2017-10-10 | General Electric Company | System and method for continuous solids slurry depressurization |
| US10018416B2 (en) | 2012-12-04 | 2018-07-10 | General Electric Company | System and method for removal of liquid from a solids flow |
| CN118430702A (en) * | 2024-07-03 | 2024-08-02 | 山东云科汉威软件有限公司 | Data fusion method based on object data model |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0486174B1 (en) * | 1990-11-16 | 1994-10-05 | Texaco Development Corporation | Process for producing high purity hydrogen |
-
1986
- 1986-06-19 DE DE8686304737T patent/DE3667180D1/en not_active Expired - Lifetime
- 1986-06-23 ES ES556464A patent/ES8801165A1/en not_active Expired
- 1986-06-23 AU AU59192/86A patent/AU586260B2/en not_active Expired
- 1986-06-23 MX MX026475A patent/MX168358B/en unknown
- 1986-06-24 PT PT82831A patent/PT82831B/en not_active IP Right Cessation
- 1986-06-24 KR KR1019860005105A patent/KR940005198B1/en not_active IP Right Cessation
- 1986-06-24 IN IN468/CAL/86A patent/IN165846B/en unknown
- 1986-06-26 CN CN86104452A patent/CN1007262B/en not_active Expired
- 1986-06-27 JP JP61149902A patent/JPH0772081B2/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102245747A (en) * | 2008-12-08 | 2011-11-16 | 通用电气公司 | Gasifier additives for improving refractory life |
| CN102245747B (en) * | 2008-12-08 | 2014-11-05 | 通用电气公司 | Gasifier additives for improving refractory life |
| CN104711026A (en) * | 2011-02-23 | 2015-06-17 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock with nickel recovery |
| CN103391989A (en) * | 2011-02-23 | 2013-11-13 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock with nickel recovery |
| CN103391989B (en) * | 2011-02-23 | 2015-03-25 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock with nickel recovery |
| CN103814118A (en) * | 2011-07-27 | 2014-05-21 | 沙特阿拉伯石油公司 | Process for the gasification of heavy residual oil with particulate coke from delayed coking unit |
| CN104302574B (en) * | 2012-03-27 | 2017-03-08 | 沙特阿拉伯石油公司 | Whole crude gasification and the integration method for generating electricity in fin panel casing gasification reactor |
| CN104302574A (en) * | 2012-03-27 | 2015-01-21 | 沙特阿拉伯石油公司 | Integrated process for the gasification of whole crude oil in a membrane wall gasifier and power generation |
| US8771550B2 (en) | 2012-04-23 | 2014-07-08 | General Electric Company | Partial oxidation feed system and method |
| CN104736681A (en) * | 2012-04-23 | 2015-06-24 | 通用电气公司 | Partial oxidation feed system and method |
| WO2013159270A1 (en) * | 2012-04-23 | 2013-10-31 | General Electric Company | Partial oxidation feed system and method |
| US10018416B2 (en) | 2012-12-04 | 2018-07-10 | General Electric Company | System and method for removal of liquid from a solids flow |
| US9702372B2 (en) | 2013-12-11 | 2017-07-11 | General Electric Company | System and method for continuous solids slurry depressurization |
| US9784121B2 (en) | 2013-12-11 | 2017-10-10 | General Electric Company | System and method for continuous solids slurry depressurization |
| CN118430702A (en) * | 2024-07-03 | 2024-08-02 | 山东云科汉威软件有限公司 | Data fusion method based on object data model |
| CN118430702B (en) * | 2024-07-03 | 2024-09-20 | 山东云科汉威软件有限公司 | Data fusion method based on object data model |
Also Published As
| Publication number | Publication date |
|---|---|
| IN165846B (en) | 1990-01-27 |
| KR940005198B1 (en) | 1994-06-13 |
| PT82831B (en) | 1991-02-08 |
| KR870000410A (en) | 1987-02-18 |
| ES556464A0 (en) | 1987-12-16 |
| AU586260B2 (en) | 1989-07-06 |
| DE3667180D1 (en) | 1990-01-04 |
| JPH0772081B2 (en) | 1995-08-02 |
| CN1007262B (en) | 1990-03-21 |
| JPS6256305A (en) | 1987-03-12 |
| ES8801165A1 (en) | 1987-12-16 |
| MX168358B (en) | 1993-05-19 |
| AU5919286A (en) | 1987-01-08 |
| PT82831A (en) | 1986-07-01 |
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