EP1377654A2 - Boucle de circulation de recyclage d'eaux usees dotee d'un gazeificateur - Google Patents
Boucle de circulation de recyclage d'eaux usees dotee d'un gazeificateurInfo
- Publication number
- EP1377654A2 EP1377654A2 EP02763905A EP02763905A EP1377654A2 EP 1377654 A2 EP1377654 A2 EP 1377654A2 EP 02763905 A EP02763905 A EP 02763905A EP 02763905 A EP02763905 A EP 02763905A EP 1377654 A2 EP1377654 A2 EP 1377654A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- black water
- water
- gasification unit
- black
- gasifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000010866 blackwater Substances 0.000 title claims abstract description 99
- 238000002309 gasification Methods 0.000 claims abstract description 54
- 238000010791 quenching Methods 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 229910001868 water Inorganic materials 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 230000003134 recirculating effect Effects 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 2
- 239000002351 wastewater Substances 0.000 abstract description 16
- 238000005201 scrubbing Methods 0.000 abstract description 12
- 238000012423 maintenance Methods 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 59
- 230000015572 biosynthetic process Effects 0.000 description 26
- 239000000446 fuel Substances 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- 239000007787 solid Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000011368 organic material Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000003079 shale oil Substances 0.000 description 3
- 239000011275 tar sand Substances 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 naphtha Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/466—Entrained flow processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/169—Integration of gasification processes with another plant or parts within the plant with water treatments
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
Definitions
- synthesis gas may be produced from combustible organic fuels, such as coal, residual petroleum, wood, tar sand, shale oil, and municipal, agriculture or industrial waste. Prior to the gasification step, these combustible organic fuels are commonly mixed with water to form slurry or emulsion. The solid combustible organic fuels, in slurry form, are then reacted with a reactive oxygen-containing gas, such as air or oxygen, and a moderator such as water or steam in a gasification reactor to obtain synthesis gas.
- a reactive oxygen-containing gas such as air or oxygen
- a moderator such as water or steam
- the combustible organic fuel is contacted with a free-oxygen containing gas, optionally in the presence of a temperature moderator such as steam or water.
- a temperature moderator such as steam or water.
- the contents will commonly reach temperatures in the range of about 1,700° F (930° C) to* about 3,000° F (1650° C), and more typically in the range of about 2,000° F (1100° C) to about 2,800° F (1540° C).
- Pressure will typically be in the range of about 1 atmosphere (100 KPa) to about 250 atmospheres (25,000 KPa), and more typically in the range of about 15 atmospheres (1500 Kpa) to about 150 atmospheres (1500 KPa).
- the synthesis gas will substantially comprise hydrogen, carbon monoxide, and lessor quantities of impurities, such as water, carbon dioxide, hydrogen sulfide, carbonyl sulfide, ammonia, and nitrogen.
- impurities such as water, carbon dioxide, hydrogen sulfide, carbonyl sulfide, ammonia, and nitrogen.
- the synthesis gas is commonly treated to remove or significantly reduce the quantity of impurities before being utilized in downstream processes.
- IGCC integrated gasification combined cycle
- the quenching process generates wastewater that must be treated for a wide range of contaminates including solids, water soluble compounds and partially water soluble compounds often referred to as "black water".
- Conventional treatment methods for the treatment of black water are expensive and thus most wastewater treatment systems are designed to store and treat no more than one day's generation of waste water.
- any significant repair to the waste water treatment system causes the entire gasification process to be shut down. For this reason there remains a need for systems that allow the continued operation of a gasification system while maintenance is being performed on the waste water treatment system.
- the present invention is generally directed to handling the raw syngas scrubbing wastewaters, or black water, from a quench gasification reactor. More particularly, the present invention describes recirculation of the black water in a recirculation loop from which at least a portion of the moderator used in the gasifier may be taken.
- the use of a recirculation loop for the black water permits the operation of the gasifier in situations such as when a source of high pressure steam is inadequate.
- the present invention also permits the service and maintenance of the black water treatment system while permitting the continued operation of the gasifier.
- a further aspect of this invention is treating the wastewater from a quench gasification reactor by recycling the wastewater to a location upstream of the gasifier.
- the wastewater is recycled back to the gasification stage, where the black water and any carbon content is mixed with liquid or pulverized solid combustible organic materials to form slurry.
- the slurry is then fed to the gasifier where it is reacted with oxygen and optional additional steam at high temperatures and pressures so as to convert any carbon contained in the wastewater, along with the combustible organic fuel, into synthesis gas.
- FIG. 1 illustrates an embodiment of the invention in schematic form. It particularly shows the recycle of the black water back to the gasifier.
- FIG. 2 illustrates an embodiment of the invention in schematic form. It particularly shows the recirculation of the black water back within a loop that can be isolated from the gasifier. DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
- Combustible organic fuel is defined as any combustible organic material such as coal, residual petroleum, wood, tar sand, shale oil, and municipal, agriculture or industrial waste. The scope of this definition is to include any combustible organic fuel that can be used in a gasification process to produce synthesis gas.
- Process water is defined as any water used to make the slurry other than the wastewater from a hydrocarbon synthesis reactor.
- the scope of the term “process water” is to include any composition of materials in which water is the predominate component.
- Slurry is defined as the combination of solid combustible organic fuel and water, where the water is process water or wastewater from a hydrocarbon synthesis reactor. See US Patents 4,887,383, 4,722,740, 4,477,259, and 4,242,098 describing some of the multitude of processes known in the art to produce slurry. The entire disclosures of the above referenced patents are hereby incorporated by reference and relied upon.
- Gasifying or “gasification” is defined as the process in which various carbonaceous fuels may be converted to synthesis gas by partial oxidation at an elevated reaction temperature and pressure.
- the carbonaceous fuel is contacted with a free- oxygen containing gas, such as air or oxygen, optionally in the presence of a temperature moderator such as steam.
- a temperature moderator such as steam.
- the contents will commonly reach temperatures in the range of about 1,700° F (930° C) to about 3,000° F (1650° C), and more typically in the range of about 2,000° F (1100° C) to about 2,800° F (1540° C).
- Pressure will typically be in the range of about 1 atmosphere (100 Kpa) to about 250 atmospheres (25,000 KPa), and more typically in the range of about 15 atmospheres (1500 Kpa) to about 150 atmospheres (1500 KPa).
- US Patent 3,945,942 describing a partial oxidation burner assembly.
- US Patent 5,656,044 describing a method and an apparatus for the gasification of organic materials.
- US Patents 5,435,940, 5,345,756, 4,851 ,013, and 4,159,238 describing a few of the many gasification processes known in the prior art. The entire disclosures of the above referenced patents are hereby incorporated by reference and relied upon.
- Synthesis gas (used interchangeably with the term “syngas”) is defined as a gaseous mixture consisting substantially of hydrogen and carbon monoxide, with lessor quantities of impurities present such as water, carbon dioxide, hydrogen sulfide, carbonyl sulfide, ammonia, and nitrogen. It is within the scope of this definition to include any synthesis gas that been treated to remove or reduce the quantity of any of the impurities, so long as the primary components are hydrogen and carbon monoxide.
- carbonaceous fuel is first obtained and prepared for feeding to a gasification reactor.
- Carbonaceous fuel is any solid, liquid, or gaseous combustible organic material that can be used as feedstock to a gasification process for produce synthesis gas production.
- the feedstock for a gasification process is usually a hydrocarbonaceous material, that is, one or more materials, generally organic, which provide a source of hydrogen and carbon for the gasification reaction.
- the hydrocarbonaceous material can be in a gaseous, liquid or solid state, or in a combination as desired, for example, a solid-liquid composition in a fluidized state.
- the feed preparation step may not be necessary, given the composition and physical nature of the feedstock.
- solid carbonaceous fuels will need to be liquefied with oil or water prior to feeding to the gasifier.
- Liquid and gaseous carbonaceous fuels may be suitable for direct feed to the gasifier, but can be pre-treated for removal of any impurities that might be present in the feed.
- liquid hydrocarbonaceous fuel as used herein to describe various suitable feedstocks is intended to include pumpable liquid hydrocarbon materials and pumpable liquid slurries of solid carbonaceous materials, and mixtures thereof.
- pumpable aqueous slurries of solid carbonaceous fuels are suitable feedstocks.
- substantially any combustible carbon-containing liquid organic material, or slurries thereof may be included within the definition of the term "liquid hydrocarbonaceous.” For example, there are:
- solid carbonaceous fuels such as coal, particulate carbon, petroleum coke, concentrated sewer sludge, and mixtures thereof
- a vaporizable liquid carrier such as water, liquid CO 2 , liquid hydrocarbon fuel, and mixtures thereof
- suitable liquid hydrocarbon fuel feedstocks to the gasifier is intended to include various materials, such as liquefied petroleum gas, petroleum distillates and residua, gasoline, naphtha, kerosine, crude petroleum, asphalt, gas oil, residual oil, tar sand oil and shale oil, coal derived oil, aromatic hydrocarbons (such as benzene, toluene, xylene fractions), coal tar, cycle gas oil from fluid-catalytic-cracking operations, furfural extract of coker gas oil, and mixtures thereof; (3) also included within the definition of the term liquid hydrocarbonaceous are oxygenated hydrocarbonaceous organic materials including carbohydrates, cellulosic materials, aldehydes, organic acids, alcohols, ketones, oxygenated fuel oil, waste liquids and by-products from chemical processes containing oxygenated hydrocarbonaceous organic materials, and mixtures thereof.
- Gaseous hydrocarbonaceous fuels that may be burned in the partial oxidation gasifier alone or along with the liquid hydrocarbonaceous fuel includes vaporized liquid natural gas, refinery off-gas, -C 4 hydrocarbonaceous gases, and waste carbon-containing gases from chemical processes.
- the carbonaceous fuel is sent to a gasification reactor, or gasifier.
- the carbonaceous fuel is reacted with a reactive free oxygen- containing gas.
- free-oxygen containing gas as used herein means air, oxygen-enriched air i.e. greater than 21 mole % O 2 , and substantially pure oxygen, i.e. greater than about 90% mole oxygen (the remainder usually comprising N 2 and rare gases).
- Substantially pure oxygen is preferred, such as that that is produced by an air separation unit (ASU).
- ASU air separation unit
- the partial oxidation of the hydrocarbonaceous material is completed, advantageously in the presence of a temperature control moderator such as steam, in a gasification zone to obtain hot synthesis gas, or syngas.
- Syngas and synthesis gas can and are used interchangeably throughout this specification.
- the need for a temperature moderator to control the temperature in the reaction zone of the gas generator depends in general on the carbon-to-hydrogen ratios of the feedstock and the oxygen content of the oxidant stream.
- a temperature moderator is commonly used with liquid hydrocarbon fuels with substantially pure oxygen. Water or steam is the preferred temperature moderator. Steam may be introduced as a temperature moderator in admixture with either or both reactant streams. Alternatively, the temperature moderator may be introduced into the reaction zone of the gas generator by way of a separate conduit in the feed injector.
- Other temperature moderators include CO -rich gas, nitrogen, and recycled synthesis gas.
- a gasification reactor generally comprises a reaction zone, made up of a vertical cylindrically shaped steel pressure vessel lined with refractory, and a quench drum, such as shown in U.S. Pat. No. 2,809,104, which is incorporated herein by reference.
- a feed injector such as shown in U.S. Pat. No. 2,928,460, which is incorporated herein by reference, may be used to introduce the feed streams into the reaction zone.
- the contents will commonly reach temperatures in the range of about 1,700° F (927° C) to 3,000° F (1649° C), and more typically in the range of about 2,000° F (1093° C) to 2,800° F (1538° C).
- Pressure will typically be in the range of about 1 atmospheres (101 kPa) to about 250 atmospheres (25331 kPa), and more typically in the range of about 15 atmospheres (1520 kPa) to about 150 atmospheres (15,199 kPa), and even more typically in the range of about 60 atmospheres (6080 kPa) to about 80 atmospheres (8106 kPa).
- US Patent 3,945,942 describing a partial oxidation feed injector assembly.
- US Patent 5,656,044 describing a method and an apparatus for the gasification of organic materials.
- US Patents 5,435,940, 4,851,013, and 4,159,238 describing a few of the many gasification processes known in the prior art. The entire disclosures of the above referenced patents are hereby incorporated by reference and relied upon.
- the hot gasification process product synthesis gas comprises carbon monoxide and hydrogen.
- Other materials often found in the synthesis gas include hydrogen sulfide, carbon dioxide, ammonia, cyanides, and particulates in the form of carbon and trace metals.
- the extent of the contaminants in the feed is determined by the type of feed and the particular gasification process utilized as well as the operating conditions.
- the hot raw effluent syngas stream leaving the refractory lined reaction zone of the partial oxidation gas generator at substantially the same temperature and pressure as in the reaction zone, less ordinary drop in the lines is directly introduced into a pool of water contained in the bottom of a quench drum or tank such as the one described in coassigned U.S. Pat. No. 2,896,927 which is herewith incorporated by reference.
- the quench drum is located below the reaction zone of the gas generator, and the stream of raw syngas which it receives carries with it substantially all of the ash and/or slag and the particulate carbon soot leaving the reaction zone of the gas generator.
- the turbulent condition in the quench drum caused by large volumes of gases bubbling up through the water helps the water to scrub much of the solids from the effluent gas.
- Large quantities of steam are generated within the quench vessel and saturate the gas stream.
- the stream of raw gas is cooled in the quench drum and leaves at a temperature in the range of about 350°F to 600°F (about 175°C to 315°C), such as about 450°F to 550°F (about 230°C to 290°C), and a pressure in the range of about 500 to 2500 psia, such as about 1000 psia.
- the quench process being carried out in the quench drum.
- the cooled and partially cleaned syngas stream leaving the quench drum is further cleaned by contact with hot scrubbing water in another gas cleaning zone.
- This gas cleaning zone may include a conventional orifice such as shown and described in coassigned U.S. Pat. No. 3,524,630 which is incorporated herein by reference and conventional venturi scrubbers and sprays, along with a gas scrubbing chamber such as shown and described in coassigned U.S.
- the stream of raw syngas is scrubbed with scrubbing water comprising hot return condensate and make-up water as described herein.
- scrubbing water comprising hot return condensate and make-up water
- the gas stream leaving the quench tank associated with the gasifier is scrubbed and intimately contacted with scrubbing water e.g. in a venturi scrubber.
- the use of a venturi scrubber in the gas cleaning zone is optional.
- the syngas passes into and up through a pool of gas scrubbing water contained in the bottom of a gas scrubbing chamber.
- the scrubbed gas is then passed up through a packed section or trays 'in the upper portion of the scrubbing chamber where it is contacted by condensate i.e. scrubbing water flowing in a downward direction.
- the syngas can optionally be subjected to further cooling and cleaning operations involving a scrubbing technique wherein the syngas is introduced into a scrubber and contacted with a water spray which further cools the syngas and removes particulates and ionic constituents from the synthesis gas.
- the initially cooled gas is then treated to desulfurize the gas prior to utilization of the synthesis gas.
- Syngas can be utilized as a fuel gas for power generation or for the synthesis of hydrocarbons in a Fischer-Tropsch operation or for use as a feedstock gas to many other different chemical process.
- One of ordinary skill in the art should appreciate and understand the value and use of syngas in the petrochemical industry.
- the amount of solid particles in the scrubbed syngas stream is reduced to very low level such as less than about 3 parts per million (ppm), and preferably less than about 1 ppm.
- ppm parts per million
- this also generates a considerable amount of waste water that is contaminated with solids, hydrocarbons and other various materials and often is referred to as "black water”.
- black water Due to clean water regulations, such water must be treated prior to release.
- Conventional treatment methods such as clarification, bioreactor treatment, filtration, centrifugation, chemical treatment and other such techniques significantly add to the cost of operation.
- many plants only have the capacity to store one day or less of this waste water before the gasification reactor must be shut down. Thus anything but minor maintenance on the waste water treatment system causes the entire system to be shut down.
- the present invention resolves the above problems by using a recycle loop in which the black water is passed though a recycle loop. It is further contemplated that at least a portion of the moderator water can be drawn from the recycle loop of the black water. In such embodiments the use of the black water as a source of moderator can substantially reduce the gasifier' s requirements for high pressure steam as a moderator.
- FIG. 1 illustrated is one exemplary embodiment of the present invention in schematic form.
- a quench gasification reactor 2 with a quench drum 3 produces synthesis gas 4 by the partial oxidation a hydrocarbon source 6 in the presence of an oxygen rich feed stream 8 and a moderator 10.
- the synthesis gas is quenched in the quench drum 3 and the slag generated by the gasification reaction is collected and handled by a slag handling system (not shown).
- a slag handling system not shown.
- quench water becomes contaminated with fine carbon solids, and other fine particulate materials suspended in the water, water soluble compounds and the like, it is removed from the gasifier and sent to the black water storage tank 12.
- black water As black water accumulates, it is sent to conventional water treatment facilities that may include clarification, bio-reactor treatment, filtration, centrifugation, chemical treatment and other conventional treatment processes for black water.
- the black water In order to prevent the settling out of the suspended solids, the black water is passed through a recirculation loop.
- the recirculation loop is composed of a recycle black water pump 14 which pumps the black water through a manual block valve 16 to either a recirculation valve 18 or a auto block valve 20.
- the recirculation loop for the black water is completed by opening the recirculation valve 18 and allowing of the black water to return to the black water tank 12.
- the black water returning to the gasifier can be used as the liquid portion of the hydrocarbon slurry feed or it may be used as an additional source of moderator.
- the black water is used as a source of moderator and the quality and quantity demands on the primary source of moderators (in this case high pressure steam) is significantly reduced.
- the gasifier can continue operations when the primary source of moderator (in this case high pressure steam) is incapacitated.
- the gasifier can be started up on the black water if there is careful control over the timing of the auto block valve such that the amount of black water moderator is appropriate. In other situations, the amount of black water that can be recirculated back to the gasifier will be limited and thus an alternate source of fresh feed water 22 may be included upstream of the autoblock valve. If volume of the black water and steam is not sufficient or incapacitated, it is possible to start and run the gasifier using the alternate feed water source.
- FIG. 1 is capable of operating in a manner that allows the recirculation of the black water to prevent the settling out of any suspended particles. It should also be appreciated that it is possible to pressurize the black water handling system by recirculating the black water in a closed loop system prior to the start-up of the gasifier. Thus one is able to bring the gasifier on-line under more stable conditions than is the current practice.
- FIG. 2 illustrates another exemplary embodiment of the invention in schematic form. It particular, FIG. 2 shows the recirculation of the black water back within a loop that can be isolated from the gasifier. It should be noted that items having the same functional role have been given the same reference number in FIG. 2 as they were given in FIG. 1.
- a quench gasification reactor 2 produces synthesis gas 4 by the partial oxidation a hydrocarbon source 6 in the presence of an oxygen rich feed stream 8 and a moderator 10.
- the synthesis gas is quenched in the quench drum 3 and the slag generated by the gasification reaction is collected and handled by a slag handling system (not shown).
- a slag handling system (not shown).
- quench water becomes contaminated with fine carbon solids, and other fine particulate materials suspended in the water, water soluble compounds and the like, it is removed from the gasifier and sent to the black water storage tank 12.
- black water As black water accumulates, it is sent to conventional water treatment facilities that may include clarification, bio-reactor treatment, filtration, centrifugation, chemical treatment and other conventional treatment processes for black water.
- the black water is passed through a recirculation loop.
- the recirculation loop is composed of a recycle black water pump 14 which pumps the black water through a first manual block valve 16 to either a recirculation valve 18 or a second manual block valve 24.
- the recirculation loop for the black water is completed by opening the recirculation valve 18 and allowing at least a portion of the black water to return to the black water tank 12.
- one can open the first manual block valve 16 close the second manual block valve 24 and open the recirculation valve 18 and establish a closed loop recirculation of the black water.
- the second manual block valve can be opened thus permitting the circulation of black water to the gasifier, via the auto block valve 20.
- the black water returning to the gasifier can be used as the liquid portion of the hydrocarbon slurry feed or it may be used as an additional source of moderator.
- the black water is used as a source of moderator and the quality and quantity demands on the primary source of moderators (in this case high pressure steam) will be significantly reduced.
- the gasifier can continue operations when the primary source of moderator (in this case high pressure steam) is incapacitated.
- the gasifier can be started up on the black water if there is careful control over the timing of the auto block valve such that the amount of black water moderator is appropriate.
- the gasifier can be operated independently of the black water system. That is to say the alternate feed water source can be used to provide the moderator water needed by the gasifier. This can be beneficial during the start up or shut down of the gasifier, or when maintenance on the black water handling system is needed.
- the recycle black water pump can be isolated from the gasifier by double isolation which would allow maintenance on the black water pump whie the gasifier is still running. It should be noted that the amount of black water that can be recirculated back to the gasifier may be limited and thus can be balanced with the alternate source of fresh feed water 22.
- the ability to isolate the black water circulation system is important for both maintenance purposes and operation of the gasifier.
- the black water recirculation system can be isolated, maintenance on the system can be conducted without having to shut down the gasifier.
- the only practical limit to such operation is the ability to store and /or treat any generated black water.
- the above illustrative embodiment also permits the start up of the gasifier on an alternate feed water source and then bring on-line the black water under pressure. This is possible because of the ability to recirculate and thus pressurize the black water recirculation loop.
- Another advantage of the present invention is that it permits the continuous recirculation of the black water in a closed loop system. This prevents the settling out of any suspended solids in the black water during time in which recycle of the black water to the gasifier is not desired. For example, when the gasifier is not running.
- wastewater from a gasification reactor can be recirculated in a recycle loop such that at least a portion of the waste water can be sent to a gasification reactor and thus used as a moderator.
- a recycle loop such that at least a portion of the waste water can be sent to a gasification reactor and thus used as a moderator.
- the wastewater can be disposed of with no adverse environmental affects.
- the large capital and operating costs associated with traditional water treatment facilities may be drastically reduced, if not eliminated.
- the on-site requirements for high pressure steam as the source of moderator can be substantially reduced and the reliability of gasifier operations may be enhanced.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Industrial Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Water Treatments (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28224201P | 2001-04-06 | 2001-04-06 | |
| US282242P | 2001-04-06 | ||
| PCT/US2002/010331 WO2002081600A2 (fr) | 2001-04-06 | 2002-04-03 | Boucle de circulation de recyclage d'eaux usees dotee d'un gazeificateur |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1377654A2 true EP1377654A2 (fr) | 2004-01-07 |
Family
ID=23080640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02763905A Withdrawn EP1377654A2 (fr) | 2001-04-06 | 2002-04-03 | Boucle de circulation de recyclage d'eaux usees dotee d'un gazeificateur |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1377654A2 (fr) |
| JP (1) | JP2004532105A (fr) |
| KR (1) | KR20030087061A (fr) |
| CN (1) | CN1500135A (fr) |
| AR (1) | AR033124A1 (fr) |
| CA (1) | CA2442060C (fr) |
| WO (1) | WO2002081600A2 (fr) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010040763A2 (fr) * | 2008-10-08 | 2010-04-15 | Shell Internationale Research Maatschappij B.V. | Procédé de préparation d’un mélange gazeux d’hydrogène et de monoxyde de carbone |
| CN103013572B (zh) * | 2011-09-28 | 2015-08-12 | 通用电气公司 | 气化煤的装置和方法 |
| PE20141956A1 (es) | 2012-03-30 | 2014-12-01 | Akzo Nobel Chemicals Int Bv | Metodo de preparacion y estacion para soluciones de agente no aglomerante |
| CN103361135B (zh) * | 2012-03-30 | 2015-10-07 | 通用电气公司 | 钢厂发电装置和方法 |
| US9656863B2 (en) | 2012-12-20 | 2017-05-23 | Air Products And Chemicals, Inc. | Method and apparatus for feeding municipal solid waste to a plasma gasifier reactor |
| JP6122664B2 (ja) * | 2013-03-05 | 2017-04-26 | 三菱重工業株式会社 | ガス精製装置およびガス精製方法 |
| KR102089107B1 (ko) * | 2013-08-16 | 2020-03-13 | 한국전력공사 | 계면활성제를 이용한 합성가스 내 불순물 제거장치 및 방법 |
| CN103965966B (zh) * | 2014-04-23 | 2015-10-21 | 中国华能集团清洁能源技术研究院有限公司 | 一种带有机废水处理的干粉加压气化装置 |
| CN107001090B (zh) * | 2014-12-12 | 2022-02-18 | Bl 科技公司 | 具有水处理和再利用的气化系统 |
| CN106765209A (zh) * | 2017-03-03 | 2017-05-31 | 中国人民解放军63729部队 | 一种四氧化二氮废液的处理装置及方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3232727A (en) * | 1961-12-13 | 1966-02-01 | Texaco Inc | Synthesis gas generation |
| US3929429A (en) * | 1974-09-26 | 1975-12-30 | Texaco Inc | Fuel gas from solid carbonaceous fuels |
| DE2828562C3 (de) * | 1978-06-29 | 1980-12-11 | Ruhrkohle Ag, 4300 Essen | Schlackenaustrag |
| US4465496A (en) * | 1983-01-10 | 1984-08-14 | Texaco Development Corporation | Removal of sour water from coal gasification slag |
| US5104419A (en) * | 1990-02-28 | 1992-04-14 | Funk Harald F | Solid waste refining and conversion to methanol |
| US6086722A (en) * | 1996-07-17 | 2000-07-11 | Texaco Inc. | Minimizing evaporator scaling and recovery of salts during gasification |
| US6610112B1 (en) * | 1999-12-07 | 2003-08-26 | Texaco Inc. | Method for oil gasification |
-
2002
- 2002-04-03 CA CA2442060A patent/CA2442060C/fr not_active Expired - Fee Related
- 2002-04-03 KR KR10-2003-7013076A patent/KR20030087061A/ko not_active Withdrawn
- 2002-04-03 WO PCT/US2002/010331 patent/WO2002081600A2/fr not_active Ceased
- 2002-04-03 EP EP02763905A patent/EP1377654A2/fr not_active Withdrawn
- 2002-04-03 JP JP2002579967A patent/JP2004532105A/ja not_active Withdrawn
- 2002-04-03 CN CNA028077040A patent/CN1500135A/zh active Pending
- 2002-04-05 AR ARP020101266A patent/AR033124A1/es not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO02081600A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030087061A (ko) | 2003-11-12 |
| WO2002081600A2 (fr) | 2002-10-17 |
| AR033124A1 (es) | 2003-12-03 |
| CA2442060A1 (fr) | 2002-10-17 |
| CN1500135A (zh) | 2004-05-26 |
| WO2002081600A3 (fr) | 2003-02-27 |
| JP2004532105A (ja) | 2004-10-21 |
| CA2442060C (fr) | 2011-08-09 |
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