CN87104309A - The method of removing sulphur compound when the carbonaceous solids particle gasifies in the fluidized-bed - Google Patents
The method of removing sulphur compound when the carbonaceous solids particle gasifies in the fluidized-bed Download PDFInfo
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- CN87104309A CN87104309A CN87104309.2A CN87104309A CN87104309A CN 87104309 A CN87104309 A CN 87104309A CN 87104309 A CN87104309 A CN 87104309A CN 87104309 A CN87104309 A CN 87104309A
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- 239000007787 solid Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000005864 Sulphur Substances 0.000 title claims abstract description 53
- -1 sulphur compound Chemical class 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 title claims description 40
- 239000007789 gas Substances 0.000 claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 238000002309 gasification Methods 0.000 claims abstract description 27
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003245 coal Substances 0.000 claims description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 28
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 19
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 19
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 claims description 16
- 229940051851 sulfurated lime Drugs 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000000567 combustion gas Substances 0.000 abstract description 19
- 230000008859 change Effects 0.000 abstract description 14
- 239000003575 carbonaceous material Substances 0.000 abstract description 8
- 230000002939 deleterious effect Effects 0.000 abstract description 6
- 238000004581 coalescence Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 24
- 235000019738 Limestone Nutrition 0.000 description 10
- 239000006028 limestone Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 240000006909 Tilia x europaea Species 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
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- 239000000571 coke Substances 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- Treating Waste Gases (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Industrial Gases (AREA)
Abstract
In fluidized-bed, coalescent emission type reactor during the gasification of carbonaceous material, remove the sulphur compound in the gasification product gas and deleterious, unsettled sulphur compound changed into surrounding environment is acceptable, the method for form that can safe handling, the particulate state sulphur-fixing agent is sent in the ash content coalescence type fluidized bed combustion gas generator with the carbon-containing feeding solids, and with fluidized-bed in the gaseous sulfur compound that under reduced state, forms during the gasification feed solids react.Then, will under gasifier, change stable, the acceptable solid of surrounding environment in the oxide regions into, and emit with ash content with the unstable sulphur compound that sulphur-fixing agent reaction forms.
Description
What the present invention relates to is in the fluidized-bed solid carbonaceous substance of having improved, coal for example, gasification process.Further say, what the present invention relates to is in fluidized-bed and at least one selectivity solids take-off pipe, change the harmful and/or unsettled sulphur compound that forms between pneumatolytic stage into surrounding environment acceptable sulphur compound on the spot, thereby reduce the method for the sulphur compound in the product gas.Solid carbonaceous substance is the substitute energy of Sweet natural gas and crude oil, but carbonaceous material, for example coal can have high relatively sulphur content.Between pneumatolytic stage, the sulphur compound that is present in the carbon-containing feeding thing generally changes deleterious gaseous sulfur compound in the sulfuration bed bioreactor.The invention provides the method for removing this unwanted gaseous sulphur compound, change this gaseous sulfur compound into surrounding environment acceptable solid form in fluidized-bed and solids take-off pipe, this solid sulfur compound can emit safely with the coal particle that exhausts.
Solid carbonaceous substance, coal for example, can be generally about 1400 ° to the high temperature of 2000 scopes and the high pressure with steam and oxygen-containing gas, air for example, contact and gasifying.The product of gasification reaction comprises hydrogen, carbon monoxide, carbonic acid gas, hydrocarbon polymer, for example methane, and sulphur compound, for example hydrogen sulfide and carbonyl sulfide.
The best approach of coal gasification is Inst. of Gas Technology (Institute of Gas Technology in Chicago, the Ill in Chicago, Illinois.) the U-GAS method that proposes.(referring to " the 51st page of oil and gas magazine (the Oil and Gas Journal) on August 1st, 1977 etc., it is for referencial use to quote the document here).The ultimate principle of this gasification and most preferred embodiment are disclosed by No. 4315758, United States Patent (USP), and it is for referencial use to quote the document here.The U-GAS method can produce purified from coal, the about 150-300 Btu/ of the acceptable low Btu(of surrounding environment standard cubic feet) fuel gas.This gas can directly use for the industry and commerce user, or uses as the surrogate of Sweet natural gas or oil fuel.The product of U-GAS method with the form of synthetic gas, can be used as chemical feedstocks and uses, or use as the thermal reduction gas body source, and with metallic ore, for example iron ore is reduced to base metal.
Disclosed U-GAS method in No. 4315758, the United States Patent (USP) overcome the soot particle agglomeration problem in the fluidized-bed gasification district in its patent of quoting as proof, but this method need be removed poisonous sulphur compound from product gas stream.The sulphur compound that is present in the carbon-containing feeding thing generally changes gaseous hydrogen sulfide and carbonyl sulfide between the pneumatolytic stage in fluidized-bed reactor.Act as a fuel before gas uses in product gas stream, or product gas stream is used for must removing these sulphur compounds before SNG production, the ammonia synthesis etc. from product gas stream, preventing the formation of deleterious oxysulfide, or avoids poisoning synthetic catalyst.A kind of traditional method of removing sulphur compound from the product gas of gasification is that product gas is cooled near envrionment temperature, and purifies with chemistry or physical absorbent.Because this method causes the remarkable reduction of process efficiency, needs increase equipment, and produces a large amount of waste materials, from several respects, this method is unsatisfactory.
As everyone knows, be that the material on basis contacts with stack gas in order to Wingdale, can remove the oxysulfide in the stack gas of coal combustion generation.Can leave directly the finely disintegrated Wingdale being sprayed in the roasting kiln somewhere of flame, perhaps can in fixed bed, moving-bed or fluidized-bed, use particulate state Wingdale or rhombspar, be used for contacting and absorbing the oxysulfide gas that contains in the flue gas stream.Everybody knows that also the burning of the coal of sulfur-bearing or oil can be carried out in the Wingdale fluidized-bed, the oxysulfide gas that produces during Wingdale and the burning reacts.Yet owing to need excessive oxygen-containing gas in the combustion reactor, impelling perfect combustion, and the gasification of carbonaceous solids particle is finished under reduced state, and the burning of coal reaction conditions is remarkable different with the gasification reaction conditions of coal or carbonaceous solids.Because oxidizing condition is provided in combustion reactor, the sulphur compound that exists changes sulfur dioxide gas into, this sulfur dioxide gas and Wingdale reaction generate calcium sulfate, and this is a kind of stable solids, do not need further processing before with its discharging.
With alkaline earth metal oxide, for example roasting Wingdale or roasting rhombspar, the patent of sending into No. 3969089, United States Patent (USP) together with the coal charging and being quoted as proof is described the sort ofly to be had in the coal gasifier of dividing fabric swatch equally, reduces the sulphur compound in the gasification product gas.Hydrogen sulfide that forms during coal gasification and carbonyl sulfide gaseous compound and calcium oxide reaction generate the solid sulfurated lime.Yet sulfurated lime is unsettled, has at atmospheric pressure state can decompose under the situation of water to generate hydrogen sulfide, and this is a kind of toxic gas.The roasting Wingdale that has vulcanized is regenerated in a revivifier discrete, that move under the state of oxidation, forms sulfur dioxide gas and calcium oxide.Because this additional treatment step needs discrete reactor, and need be with the hot solids particle of anhydrous state from a container transport to another container, its result causes the reduction of process efficiency, and causes producing oxysulfide, is very unfavorable and oxysulfide is discharged into the atmosphere.United States Patent (USP) has described coal for No. 3970434 and alkaline earth metal oxide mixes the back gasification, absorbs sulphur, makes the alkaline earth sulfide burning then in discrete device.United States Patent (USP) has then been described gasification of coal under the situation that aerobic, oxyhydroxide, supercarbonate, alkaline carbonate or alkaline earth metal carbonate exist for No. 3977844, form metallic sulfide, this metallic sulfide is transported to a discrete reactor, change it into gaseous hydrogen sulfide, this gaseous hydrogen sulfide can be used in Crouse (Claus) process technology.
The purpose of this invention is to provide a kind of method of removing sulphur compound, this sulphur compound is that carbonaceous material discharges between pneumatolytic stage in fluidized-bed, this method is in the fluidized-bed and selectivity solids take-off pipe in a reaction vessel, to change deleterious and/or unsettled sulphur compound into surrounding environment acceptable sulphur compound.
Another object of the present invention is that carbonaceous material is gasified in a kind of coalescent emission type fluidized-bed, the gaseous sulfur compound that will form between pneumatolytic stage in the main body of fluidized-bed changes the solid sulfur compound into, and in the coalescent discharge region of fluidized-bed, change unsettled solid sulfur compound into stable solid sulfur compound, and emit together with ash content.
Method of the present invention can be used for any suitable ash content coalescence type fluidized bed combustion gas generator, and for example United States Patent (USP) No. 3935825, No. 4229289 and No. 4315758 described fluidized bed combustion gas generators are quoted these United States Patent (USP)s here with for referencial use.The carbon-containing feeding solids that can be gasified and form cindery the sort of type can spray in the sealed fluidized bed combustion gas generator by the gate magazine-less system.In fluidized-bed, carbonaceous solids particle and steam and oxygen-containing gas reaction, gasification rapidly generates the product gas mixture that contains hydrogen, carbon monoxide, carbonic acid gas, water, methane, hydrogen sulfide, carbonyl sulfide and a little impurity.Gasification is main temperature required and ash content maintained no slagging scorification state is temperature required to be finished down, generally about 800 °F to about 2000 °F according to the type of carbon-containing feeding thing.According to the type of carbon-containing feeding thing and the end-use of product gas, fluidized-bed is forced into about 15 to 750 pounds/inch
2For example, for the production of industrial fuel, minimum pressure is about 20 to about 50/ inch
2Be optimal.Because the generation of hydrogen is kept reduced state in the major portion of whole fluidized-bed.The result of reduced state makes the sulphur that exists in nearly all carbon-containing feeding thing change gaseous hydrogen sulfide and carbonyl sulfide into.Hydrogen sulfide generally is about 20: 1 with the ratio of carbonyl sulfide.
The porous inclination grid gas distribution grid of the fluidizing gas that contains steam and contain a small amount of oxygen or oxygen-free gas below fluidized-bed introduced fluidized-bed.Taking-up gas with elevated oxygen level is introduced the fluidized bed combustion gas generator by the solids withdrawing device, and the solids withdrawing device comprises (Venturi) sorter system in the venturi that is arranged on below the grid distributor.In these two gas inlet tubes, the ratio of oxygen and steam should strictly be monitored and control, and the gas of introducing sorter in the venturi has higher oxygen, steam ratio substantially.Thereby, keep comparatively high temps at the bottom center position of fluidized-bed, impel the particle caking of high ash content concentration, these agglomerated grains are discharged by sorter in the venturi under action of gravity, and emit from fluidized-bed.Such ash content coagulation type fluidized bed combustion gas generator has reached low-level carbon loss in the ash content of discharging, reached very high carbon total conversion rate, is using under the situation of coal, and the carbon total conversion rate is 95% or higher.The particulate that takes out from gasifier top with product gas can be separated with product gas in any suitable gas-solid separator, and these particulates are returned to the fluidized bed combustion gas generator again.
The method according to this invention, a kind of sulphur-fixing agent is sent in the fluidized bed combustion gas generator with the carbon-containing feeding thing, is used for removing the sulphur compound that the carbon-containing feeding thing formed between pneumatolytic stage, and gaseous sulfur is changed into solid-state, this solid-state sulphur is that surrounding environment is acceptable, but and safe handling.The sulphur-fixing agent that is suitable for using in the method for the invention comprises Wingdale, rhombspar, metal carbonate, metal oxide and their composition.The Wingdale of pulverizing is a kind of sulphur-fixing agent of the best, and is because it obtains easily, abundant and inexpensive.Sulphur-fixing agent, for example the Wingdale of Fen Suiing can be stored in the discrete feed gate hopper, mixes with the carbon-containing feeding solids in common feed pipe, and sprays into the fluidized bed combustion gas generator.Send into the amount of the sulphur-fixing agent of gasifier is determined by the amount of the sulphur that exists in the carbon-containing feeding with the carbon-containing feeding thing.Metal in the sulphur-fixing agent, calcium for example is generally about 1 to about 5 with the mol ratio of sulphur in the carbon-containing feeding, and the best is about 1.5 to 3.Select ideal sulphur-fixing agent granular size, make that sulphur-fixing agent particle and carbon-containing feeding have the roughly the same residence time in the fluidized bed combustion gas generator, and make the sulphur compound solid particulate emit by sorter in the venturi of fluidized-bed bottom with the ash content caking.
Use the Wingdale of pulverizing as sulphur-fixing agent, because the high temperature in the fluidized-bed, at Wingdale (CaCO
3) send into gasifier in very short time afterwards, just resolve into solid oxide calcium and gaseous carbon dioxide.Solid oxide calcium and react according to following reaction formula then from sulphur compound, gaseous hydrogen sulfide and carbonyl sulfide that the carbon-containing feeding thing forms:
Like this, because dominant reduced state in the main body of fluidized-bed, the gaseous sulfur compound that forms from the carbon-containing feeding thing changes solid-state sulfurated lime into.Because the gaseous product of gasification directly mixes with superfluous lime stone in the fluidized-bed, the basic thermodynamic change fully of hydrogen sulfide in the fluidized bed combustion gas generator and carbonyl sulfide is a sulfurated lime.
Hydrogen sulfide and carbonyl sulfide are subjected to the restriction of vapor partial pressure in the fluidized bed combustion gas generator to the transformation of sulfurated lime, so it is desirable to reduce the vapor partial pressure in the gasification product gas, change sulfurated lime substantially fully into the sulphur compound that will form between pneumatolytic stage.In addition, lower temperature and higher concentration of hydrogen sulfide help to reach gaseous sulfur compound ideal transformation balance.Thereby for having high sulfur content and need be than the carbon-containing feeding thing of low operating temperature, the efficient that gaseous sulfur compound changes sulfurated lime into is higher.
When the sulfurated lime solids by fluidized-bed downwards towards fluidized-bed bottom and during the motion of selectivity ash content caking take-off pipe, they run into the well-oxygenated environment at fluidized-bed bottom and selectivity take-off pipe place, this well-oxygenated environment is sent into high-load relatively oxygen by sorter take-off pipe in the venturi and is caused, to impel the ash content caking.When the motion of bottom sulfurated lime passes through this fluidized-bed and the thermooxidizing district on take-off pipe top, according to following reaction formula, sulfurated lime and oxygen reaction generate solid-state calcium sulfate:
Temperature, residence time and the well-oxygenated environment at place, solids take-off pipe top are such in fluidized-bed bottom and the selectivity venturi, and it makes basic all sulfurated limes all change calcium sulfate into.Calcium sulfate is a kind of solid-state, stable, acceptable compound of surrounding environment, and it can discharge from delivery pipe with solid form with coalescent ash content and unreacted Wingdale.Because sulphur has solidified and existed with the form that environment is not produced harm, calcium sulfate can discharge with ash content caking and unreacted Wingdale.
With reference to the most preferred embodiment that describes below and in conjunction with the accompanying drawings, the present invention's characteristic recited above and further feature, and obtain the mode of these characteristics will be clearer, the present invention can be more readily understood.Accompanying drawing has schematically shown a fluidized-bed fuel gas generator device that is applicable to the embodiment of the inventive method.
As shown in the figure, fluidized bed combustion gas generator 2 comprises a single-stage fluidized bed gasifying reactor, and this reactor can be in about 800 to 2000 temperature, and the best is about 1400 °F to 2000 °F, and pressure is about 15 to 1000 pounds/inch
2Condition under move.
The carbon-containing feeding thing that is applicable to the inventive method comprises any sulfur-bearing carbonaceous material of gasifying of being easy in coalescent ash content emission type fluidized-bed, comprise different sorts and other coal of level, resinous shale, refinery coke, mud coal, brown coal, solid waste and solid-state organism.Coal is good especially carbon-containing feeding thing, and the detailed description to most preferred embodiment will only relate to coal below, but for suitable carbon-containing feeding thing, method of the present invention is not limited in coal.
The coal of pulverizing was delivered to feed gate hopper 8 from feed storage by solids feeding line 6 before sending into fluidized bed combustion gas generator 2, do not need to give to handle the coal solids earlier and/or slough fugitive constituent.Generally the charging solids are crushed to mean diameter less than about 1/4 inch size.
Before sulphur-fixing agent is sent into fluidized bed combustion gas generator 2, can give first the mixing with coal, perhaps preferably be delivered to gate hopper 9 by feeding line 7 from storage.Sulphur-fixing agent also can be by any suitable feeding unit, and for example gate hopper feed system sends into fluidized-bed respectively with coal.Suitable sulphur-fixing agent comprises Wingdale, rhombspar and other metal carbonate compounds, spathic iron ore for example, metal oxide, for example oxide compound of iron and zinc, and their mixture.Wingdale is best sulphur-fixing agent, will only relate to Wingdale as sulphur-fixing agent here, and for suitable sulphur-fixing agent, method of the present invention is not limited only to Wingdale.Crushed limestone, make it to reach the particle of such size, promptly make limestone particle have the residence time roughly the same with coal particle in fluidized-bed reactor, the size of limestone particle and density can make Wingdale discharge by discharging sorter in the venturi of fluidized-bed 4 bottoms with the ash content caking.Wingdale generally is ground into mean diameter less than about 1/16 inch size.Limestone particle is carried by pipeline 11 from gate hopper 9, mixes in solids mixing tube 14 with the coal solids, sprays into fluidized-bed 4.Sending into the amount of the Wingdale of fluidized-bed 4 is determined by the sulphur content in the coal solids.Wingdale adds with certain amount, makes the mol ratio of calcium and sulphur preferably reach about 1: 1 to 5: 1, and the best is about 1.5: 1 to about 3: 1.
Fluidized-bed 4 is in the middle part in the gasifier 2, and coal wherein and limestone particle are by the fluidizing gas fluidization, and this fluidizing gas comprises the gas of steam and low oxygen content.Fluidizing gas is delivered to below the fluidized-bed by fluidizing gas inlet 38, and is distributed in whole fluidized-bed 4 by porous inclination grid 42.Have seldom or oxygen-free in the composition of fluidizing gas, form reduced state with major portion at whole fluidized-bed body.When the carbonaceous solids particle of sulfur-bearing gasified in fluidized-bed 4, sulphur compound mainly discharged from the carbonaceous solids particle with the form of gaseous hydrogen sulfide and carbonyl sulfide.Under the reduced state of fluidized-bed, lime carbonate in the limestone particle and gaseous hydrogen sulfide and carbonyl sulfide reaction generate solid oxide calcium and gaseous carbon dioxide.Because the reduced state in the fluidized-bed 4 body major portions, solid oxide calcium scatter and react with basic all gaseous hydrogen sulfide and carbonyl sulfide, generate solid-state sulfurated lime, water and carbonic acid gas in fluidized-bed 4.The speed of the taking-up gas that adjusting is sent into, making the residence time of solids in fluidized-bed 4 is about 20 minutes to about 3 hours, the best is about 1/2 to about 11/2 hour.Solid limestone particle and solid sulfurated lime and solid carbon thing ash particles in fluidized-bed 4 after the suitable residence time, move to the top of fluidized-bed 4 bottoms and selectivity take-off pipe, the there is a high-temperature oxidation environment, basic all sulfurated limes change calcium sulfate into, and sorter 40 and take-off pipe 56 emit in venturi at last.
Solids sorter 40 includes the tapered portion 46 that stretches upwards expansion in the selectivity venturi, the tapered portion 48 of narrow middle part 44 and stretching, extension expansion downwards, and the inlet of the tapered portion 46 that makes progress is arranged on the bottom of inclination grid 42.The solids that comprise steam and oxygen-containing gas take out gas and send into the following take-off pipe 56 below the sorter 40 in the venturi by gas inlet 52.Solids take out the oxygen that gas contains higher concentration, and its scope is about 5% to 50%, and the best is about 5% to 25%(volume), to form well-oxygenated environment in the lower bottom part that in selectivity solids sorter 40, reaches fluidized-bed 4.By this way, keep comparatively high temps in fluidized-bed 4 bottom lower areas, the high ash content concentration particle that impels the gasification of carbon-containing feeding thing to form lumps under the temperature near the initial softening temperature of ash particles.Ash particles is coalescent, and the mobile taking-up gas that makes progress no longer can be supported them until taking out sorter 40 through selectivity, and then, the ash content caking takes out sorter 40 by selectivity under action of gravity and take-off pipe 56 takes out.Solids are through any suitable reliever then, and for example suitable gate hopper 61 emits by reactor delivery pipe 60.In the dominant fluidized-bed of state of oxidation bottom and the high-temperature zone at tapered portion 46 places that stretch upwards of selectivity take-off pipe 40 impel sulfurated lime and molecular oxygen reaction generation calcium sulfate.The state of oxidation of tapered portion 46 that stretches upwards and fluidized-bed bottom makes basic all sulfurated limes change the calcium sulfate that is set in the limestone particle into, and its proportion/size is suitable for discharging through selectivity solids sorter 40 with ash content caking and unreacted limestone particle.The residence time of particle in the following oxidation zone of fluidized-bed 4 and the tapered portion 46 that stretches upwards is preferably about 3 to 20 minutes, and the best is about 5 to 10 minutes.
Gaseous state stack gas process gasifier upper space 5, and pass through gaseous state flue gas emissions pipe 20 and from fluidized bed combustion gas generator 2, discharge.Gaseous state stack gas contains the mixture of product gas and the coal dust of carrying under one's arms, and this gaseous state stack gas is transported in the suitable solids/gas separator, for example first section cyclonic separator 22.In cyclonic separator 22, diameter is that about 20 to 250 microns big pulverized coal particle is separated from product gas, and turns back in the fluidized-bed 4 by first section recirculation pipe 24.Product gas is transported in second solids/gas separator through first section flue pipe 26 then, second section cyclonic separator 28 for example, here diameter is about 5 to separate from product gas to other about 100 microns dust granules, and these particles turn back in the fluidized-bed 4 through second section recirculation pipe 32.Carry the product gas that has removed most of coal dust of from fluidized-bed 4, taking out of by product gas pipeline 30, use, or be used for SNG production, ammonia synthesis or the like with the gas that acts as a fuel.
Therefore, the invention provides in an independent ash content coalescence type fluidized bed combustion gas generator and from the product gas of coal, remove sulphur compound, and the method that deleterious and/or unsettled sulphur compound is changed into the acceptable form of surrounding environment.The following examples only are for illustrative purposes, are not to limit the present invention by any way.
Embodiment
The method according to this invention, in as shown in the figure fluidized bed combustion gas generator substantially, gasification contains about 0.6%(weight) the Utah State bituminous coal of sulphur (being equivalent to has 450ppm hydrogen sulfide in gasifier).In altogether during 12 hours, comprise 7 hours steady operational status, with 1215 Pounds Per Hours speed the coal pulverized and 65 Pounds Per Hours speed are sent the Wingdale of pulverizing into gasifier.The coal charging has the size of average 6 orders (U.S. sieve screen distance), and the Wingdale charging has the size of average 60 orders (U.S. sieve screen distance).The gasifier operating temperature is about 1800 °F, and operating pressure is about 45 pounds/inch
2Fluidizing gas comprises air and steam, to produce the product gas of low Btu value.Send into and contain the taking-up gas that volume percent is 8 oxygen, and with the speed of per second 33 Foot through selectivity take-off pipe necking part.The existence of Wingdale neither influences the gasification of the product gas that produces satisfaction and the conversion process of carbon, does not also influence the ash content coalescence effect of gasifier.Ash content caking takes out with selectivity take-off pipe in solidifying in the calcium sulfate of Wingdale and unreacted Wingdale from venturi.
At the fluidized-bed run duration, in fluidized-bed and venturi, take out sample the selectivity take-off pipe.These samples show, sulphur mainly exists with the form of sulfurated lime (CaS) in fluidized-bed, and in venturi in the selectivity take-off pipe, sulphur is mainly with calcium sulfate (CaSO
4) form exist, calcium sulfate is a kind of stable, acceptable sulphur compound of surrounding environment.These results prove, in independent ash content coalescence type fluidized bed combustion gas generator, change the deleterious and/or unsettled gaseous sulfur compound that produces during the coal gasification into surrounding environment acceptable solid form really.
In the superincumbent specification sheets, invention has been described by most preferred embodiment, many details have been stated for purposes of illustration, to one skilled in the art, be apparent that, under the situation that does not break away from ultimate principle of the present invention, the present invention admits of other embodiments, and some details described herein also can change.
Claims (24)
1, the method for the carbon-containing feeding solids of gasification sulfur-bearing in the single-stage fluidized bed in single-stage gasifying reactor with density/big or small selectivity solids take-off pipe, this method comprises:
The carbon-containing feeding solids of the sulfur-bearing that is easy to gasify and the sulphur-fixing agent particle that selects from metal carbonate, metal oxide and their mixture are sent into described single-stage fluidized bed;
Under about 800 to 2000 temperature, the carbon-containing feeding solids of the described sulfur-bearing of gasification in described fluidized-bed, generate ash content and product gas, form the reduction zone in the major portion of described single-stage fluidized bed, described product gas contains gaseous sulfur compound;
Described gaseous sulfur compound is reacted, solid metal sulphur compound in the middle of generating in the reduction zone of described single-stage fluidized bed with the oxide compound of described sulphur-fixing agent;
Send into oxygen by described selectivity solids take-off pipe, keep oxide regions in described fluidized-bed bottom and described selectivity solids take-off pipe top, in this oxide regions, make described in the middle of the reaction of solid metal sulphur compound, generate stable, the acceptable particulate state sulfocompound of surrounding environment;
Take out product gas from the upper space of described single-stage gasifying reactor, in this product gas, removed described gaseous sulfur compound substantially; With
From described single-stage fluidized bed, take out described ash content and described stable, the acceptable particulate state sulfocompound of surrounding environment by described selectivity solids take-off pipe.
2, method according to claim 1, wherein said carbon-containing feeding solids comprise coal.
3, method according to claim 1, wherein said sulphur-fixing agent particle are to choose the oxide compound of oxide compound, zinc from Wingdale, rhombspar, spathic iron ore, iron and their mixture.
4, method according to claim 1, wherein said sulphur-fixing agent particle are to choose from lime carbonate, calcium oxide and their mixture.
5, method according to claim 4, wherein said gaseous sulfur compound comprises hydrogen sulfide and carbonyl sulfide; Described intermediate particle shape sulphur compound comprises sulfurated lime; Described stable, the acceptable particulate state sulfocompound of surrounding environment comprises calcium sulfate.
6, method according to claim 4, wherein sending into the calcium of described fluidized-bed and the mol ratio of sulphur is about 1: 1 to about 5: 1.
7, method according to claim 4, wherein sending into the calcium of described fluidized-bed and the mol ratio of sulphur is about 1: 5 to 3: 0.
8, method according to claim 1, wherein said sulphur-fixing agent particle provides with certain amount, so that the mol ratio of metal and sulphur reaches about 1: 1 to about 5: 1 in described fluidized-bed.
9, method according to claim 8, wherein said sulphur-fixing agent provides with certain amount, so that the mol ratio of metal and sulphur reaches about 1.5: 1 to about 3: 1 in described fluidized-bed.
10, method according to claim 1 wherein contains oxygen taking-up gas and offers described fluidized-bed by described selectivity solids take-off pipe, forms described oxide regions in described fluidized-bed bottom and described selectivity solids take-off pipe.
11, method according to claim 10, the wherein said oxygen that contains takes out gas to contain volume percent is about oxygen of 5 to 50.
12, method according to claim 1, wherein the residence time of solids in the described reduction zone of described fluidized-bed is about 1/3 hour to about 3 hours.
13, method according to claim 1, wherein the residence time of solids in the described reduction zone of described fluidized-bed is about 1/2 hour to about 1 1/2 hours.
14, method according to claim 1, wherein the residence time of solids in described oxide regions is about 3 to 20 minutes.
15, method according to claim 1, wherein the residence time of solids in described oxide regions is about 5 to 10 minutes.
16, method according to claim 1, wherein said carbon-containing feeding solids comprise coal; Described sulphur-fixing agent particle is to choose from lime carbonate, calcium oxide and their mixture; Sending into the calcium of described fluidized-bed and the mol ratio of sulphur is about 1: 1 to about 5: 1; The described oxygen that contains takes out gas to contain volume percent is about 5 to about 50 oxygen; The residence time of solids in the described reduction zone of described fluidized-bed is about 1/3 hour to about 3 hours; The residence time of solids in described oxide regions is about 3 to 20 minutes.
17, the method for the carbon-containing feeding solids of gasification sulfur-bearing in the single-stage fluidized bed in a single-stage gasifying reactor with density/big or small selectivity solids take-off pipe, described gasification produces ash content and product gas, in the major portion of described single-stage fluidized bed, form the reduction zone, described product gas includes gaseous sulfur compound, and its improvement comprises: the sulphur-fixing agent particle that will select from metal carbonate, metal oxide and their mixture is sent into described fluidized-bed; In the described reduction zone of described single-stage fluidized bed, the oxide compound of described gaseous sulfur compound and described sulphur-fixing agent is reacted, solid metal sulphur compound in the middle of generating; And send into oxygen by described selectivity solids take-off pipe, keep an oxide regions in described fluidized-bed bottom and described selectivity solids take-off pipe top, in this oxide regions, make described in the middle of the reaction of solid metal sulphur compound, form stable, the acceptable particulate state sulfocompound of surrounding environment.
18, method according to claim 17, wherein said sulphur-fixing agent particle are to choose the oxide compound of oxide compound, zinc from Wingdale, rhombspar, spathic iron ore, iron and their mixture.
19, method according to claim 17, wherein said sulphur-fixing agent particle are to choose from lime carbonate, calcium oxide and their mixture.
20, method according to claim 19, wherein said gaseous sulfur compound comprises hydrogen sulfide and carbonyl sulfide; Described intermediate particle shape sulphur compound comprises sulfurated lime; Described stable, the acceptable particulate state sulfocompound of surrounding environment comprises calcium sulfate.
21, method according to claim 17, wherein said sulphur-fixing agent particle provides with certain amount, so that the mol ratio of metal and sulphur reaches about 1: 1 to about 5: 1 in described fluidized-bed.
22, method according to claim 17, wherein the residence time of solids in the described reduction zone of described fluidized-bed is about 1/3 hour to about 3 hours.
23, method according to claim 17, wherein the residence time of solids in described oxide regions is about 3 to 20 minutes.
24, method according to claim 17, wherein said carbon-containing feeding solids comprise coal, described sulphur-fixing agent particle is to choose from lime carbonate, calcium oxide and their mixture, sending into the calcium of described fluidized-bed and the mol ratio of sulphur is about 1: 1 to about 5: 1, the residence time of solids in the described reduction zone of described fluidized-bed is about 1/3 hour to about 3 hours, and the residence time of solids in described oxide regions is about 3 to 20 minutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86535686A | 1986-05-20 | 1986-05-20 | |
| US865356 | 1986-05-20 |
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| Publication Number | Publication Date |
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| CN87104309A true CN87104309A (en) | 1988-03-02 |
| CN1018928B CN1018928B (en) | 1992-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87104309 Expired CN1018928B (en) | 1986-05-20 | 1987-05-19 | Removal of sulfur compounds in fluidized bed carbonaceous solids gasification |
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| CN (1) | CN1018928B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034422C (en) * | 1991-07-10 | 1997-04-02 | 同济大学 | High-temp two-step desulphurization process for gas |
| CN1037693C (en) * | 1990-10-08 | 1998-03-11 | 三菱重工业株式会社 | Process for purifying high-temp. reducing gases |
| CN1092076C (en) * | 1997-06-25 | 2002-10-09 | 中国科学院化工冶金研究所 | Decoupled recirculating fluidized bed combustion system and its desulfurizing and denitrating process |
| CN103842299A (en) * | 2011-08-02 | 2014-06-04 | 瓦斯技术研究所 | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
| CN107191935A (en) * | 2011-04-22 | 2017-09-22 | 谐和能源有限责任公司 | The method that the fuel of processing and coal are gasified with cofiring altogether |
| CN109937082B (en) * | 2016-10-13 | 2022-04-01 | 菲尼克斯先进技术有限公司 | Gaseous combustible fuel containing suspended solid fuel particles |
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1987
- 1987-05-19 CN CN 87104309 patent/CN1018928B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037693C (en) * | 1990-10-08 | 1998-03-11 | 三菱重工业株式会社 | Process for purifying high-temp. reducing gases |
| CN1034422C (en) * | 1991-07-10 | 1997-04-02 | 同济大学 | High-temp two-step desulphurization process for gas |
| CN1092076C (en) * | 1997-06-25 | 2002-10-09 | 中国科学院化工冶金研究所 | Decoupled recirculating fluidized bed combustion system and its desulfurizing and denitrating process |
| CN107191935A (en) * | 2011-04-22 | 2017-09-22 | 谐和能源有限责任公司 | The method that the fuel of processing and coal are gasified with cofiring altogether |
| CN103842299A (en) * | 2011-08-02 | 2014-06-04 | 瓦斯技术研究所 | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
| CN103842299B (en) * | 2011-08-02 | 2015-10-21 | 瓦斯技术研究所 | With ammonium sulfate form removing hydrogen sulfide from hydropyrolysis Product vapors |
| CN105107346A (en) * | 2011-08-02 | 2015-12-02 | 瓦斯技术研究所 | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
| US9593282B2 (en) | 2011-08-02 | 2017-03-14 | Gas Technology Institute | Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors |
| CN105107346B (en) * | 2011-08-02 | 2017-09-08 | 瓦斯技术研究所 | Hydrogen sulfide is removed with sulfuric acid ammonium form from hydropyrolysis Product vapors |
| CN109937082B (en) * | 2016-10-13 | 2022-04-01 | 菲尼克斯先进技术有限公司 | Gaseous combustible fuel containing suspended solid fuel particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1018928B (en) | 1992-11-04 |
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