CN1026149C - Method and apparatus for co-generating power and hydrocarbons from coal derived synthesis gas using pressure swing absorption - Google Patents
Method and apparatus for co-generating power and hydrocarbons from coal derived synthesis gas using pressure swing absorption Download PDFInfo
- Publication number
- CN1026149C CN1026149C CN90108965A CN90108965A CN1026149C CN 1026149 C CN1026149 C CN 1026149C CN 90108965 A CN90108965 A CN 90108965A CN 90108965 A CN90108965 A CN 90108965A CN 1026149 C CN1026149 C CN 1026149C
- Authority
- CN
- China
- Prior art keywords
- synthetic gas
- gas
- coal
- hydrocarbon
- hydrogen
- 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.)
- Expired - Fee Related
Links
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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
-
- 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
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/006—Hydrogen cyanide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C3/00—Gas-turbine plants characterised by the use of combustion products as the working fluid
- F02C3/20—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
- F02C3/26—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension
- F02C3/28—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension using a separate gas producer for gasifying the fuel before combustion
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1643—Conversion of synthesis gas to energy
- C10J2300/165—Conversion of synthesis gas to energy integrated with a gas turbine or gas motor
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Industrial Gases (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
A process for producing hydrocarbons and power comprises partially combusting finely divided fuel to produce synthesis gas (H2/CO of 0.25-0.70) and removing particulates, HCN and H2S from the gas at 1, passing part of the gas through a pressure sealing adsorber 2 to remove CO and produce a H2-rich stream 3(H2/CO of 3 to 15), combining the H2-rich gas with part of the synthesis gas to produce a gas having a H2/CO of 1 to 3, which is used at 5 to synthesise hydrocarbons, and desorbing CO from the adsorber 2 and using it, e.g. in gas turbine 4, to produce power.
Description
The present invention relates to by prepare the method and apparatus that synthetic gas (carbon monoxide and hydrogen) generates electricity simultaneously and obtains hydro carbons with oxygen-containing gas partial oxidation carbonic solid fuels in small, broken bits.
The oxygen-containing gas that is used for partial oxidation can be pure oxygen, oxygen and mixture of steam, air or the mixture be made up of pure oxygen, air and water vapour.
Consider that crude oil is stocked and to be used up, so the synthetic gas of producing as the raw material of many Chemicals is becoming day by day interesting topic.
The partial oxidation of subdivided solids carbonaceous fuel can carry out according to various known method.
When the subdivided solids carbonaceous fuel is used to prepare synthetic gas, the subdivided solids carbonaceous fuel is in company with oxygen-containing gas partial combustion in reactor, and the liquid slag of Xing Chenging is excluded and enters water-bath by action of gravity by a slag emission device to become to play in the slag quencher of chilling solidification by the outlet of reactor bottom during this period.
The subdivided solids carbonaceous fuel with can produce the synthetic gas of mainly forming as the pure substantially oxygen generating unit divided combustion of oxygen-containing gas by carbon monoxide and hydrogen.When oxygen-containing gas was air or oxygen-rich air, formed synthetic gas contained the nitrogen of number in the majority quantitatively certainly equally.The subdivided solids carbonaceous fuel typically refers to coal or other solid fuel such as brown coal, timber, carbon deposit, peat coke etc., but the mixture of liquid or gas and granular solids fuel is suitable equally.
The suitable practice is to add negative catalyst so that make temperature retarded to the influence of reactor in reactor, and this purpose can realize by the product generation thermo-negative reaction of negative catalyst and reactant and/or synthesis gas preparation process.Suitable negative catalyst is water vapor and carbonic acid gas.
Gasification suits to carry out in the pressure range of 1200-1700 ℃ temperature range and 1～200 crust.
The reactor that is used to finish the synthesis gas preparation process can be any suitable shape.
Can adopt any suitable mode that subdivided solids carbonaceous fuel and oxygen-containing gas are added reactor, so hereinafter will be not described in detail.
Downward drippage of the liquid slag that forms in the partial combustion reaction and process are positioned at the outlet of reactor bottom and are discharged.
In the partial oxidation process of subdivided solids carbonaceous fuel such as gasification of coal, fuel is added in the gasifier by suitable carrier fluid by feeding equipment.
The someone advises carbonaceous material is converted into and can be used to produce different generated energy effectively to satisfy the gas and the liquid fuel of industry and public utilities needs.
For instance, methyl alcohol can be used as the peak postcombustion in the combined cycle generation process, but this practice has many weak points (CO-conversion, sulphur and CO
2Deep removal, produce down used heat at 100 ℃).
In addition, the someone advises by the organic molecule that forms and disassociation is suitable being that alkyl formate is caught, stored and discharge CO and can use CO as the peak postcombustion.Yet this method requires from the synthetic gas of gasifier unnecessary chemical reaction to take place further.
Yet currently known methods is not suitable for and generates electricity simultaneously effectively and prepare hydro carbons.Owing to need additional hydrogen from coal synthetic gas synthin, thus must be together with the device sets that produces hydrogen, and this descends its economic benefit.
So, one of purpose of the present invention provides is a kind ofly generated electricity simultaneously and is prepared the method and apparatus of hydro carbons by the coal synthetic gas of deriving, wherein do not need additional hydrogen production device and make power production process more flexible practical, thereby possessed the advantage that can produce tangible economic benefit and efficient.
Therefore, the invention provides a kind of utilization and in the combined cycle generation process, generate electricity simultaneously and prepare the method for hydro carbons by coal deutero-synthetic gas, comprising the following step:
A) partial combustion subdivided solids carbonaceous fuel and oxygen-containing gas make it become wherein H
2/ CO is than being the synthetic gas of 0.25-0.70;
B) handle described synthetic gas so that remove particle, HCN and H
2S;
C) with the synthetic gas that at least a portion generated, add among the pressure conversion adsorption unit, wherein most of CO is adsorbed H in the hydrogen-rich stream that is produced
2/ CO ratio range is 3-15;
D) synthetic gas that once more a hydrogen-rich stream and a part is produced by the partial combustion process merge and with this as H wherein
2/ CO ratio range is 1～3 hydrocarbon synthesis device raw material;
E) thus make the CO desorb that is adsorbed obtain wherein H
2/ CO ratio range is the rich CO logistics of 0.05-0.25, and with this raw material as power generation assembly.
The invention still further relates to a kind of utilization and in the combined cycle generation process, generate electricity simultaneously and the equipment for preparing hydro carbons by the synthetic gas of coal generation, comprising:
A) be used for partial combustion subdivided solids carbonaceous fuel and oxygen-containing gas and generation H
2/ CO ratio is the device of the synthetic gas of 0.25-0.70;
B) be used to handle described synthetic gas so that remove particle, HCN and H
2The device of S;
C) thus the synthetic gas that is used for that at least a portion is generated adds to the device that absorbs most of CO among pressure conversion absorbing unit;
D) be used for once more the device that the synthetic gas that a hydrogen-rich stream and a part are produced by the partial combustion process is merged and being used for this H
2/ CO ratio range is the device that 1～3 merging stream feed is transported to the hydrocarbon synthesis unit.
E) be used for CO that desorb is adsorbed so that obtain its H
2/ CO ratio range is the device that is rich in the CO logistics of 0.05-0.25 and the device that is used for it is sent to as raw material generator unit.
Like this, under the condition that needn't adopt the required additional hydrogen production apparatus of synthetic hydrocarbon, just can in generating, prepare hydro carbons.
Describe the present invention below with reference to the accompanying drawing of numerical value representation block-diagram wherein in detail by embodiment.
According to the present invention, the gasifier carbonaceous feed such as coal, brown coal, petroleum residue under suitable condition, adopt mainly by oxygen forms, when condition is possible and the vaporized chemical combined of water vapor gasified.
Synthetic gas mainly contains carbon monoxide and hydrogen, also has amounts of carbon dioxide, methane, hydrogen sulfide, argon and other rare gas element simultaneously.H
2/ CO ratio range is 0.25-0.70.
The present invention is based on following thought finishes.
Generating needs combustible gas.The per-cent of hydrogen is unimportant.Every mole of calorific value comparing carbon monoxide with hydrogen is higher, thereby more suitable.The H of the synthetic required synthetic gas of valuable hydro carbons
2/ CO ratio is about 2.
If select for use pressure conversion to absorb the connecting link of (PSA) device between synthesizing as gasifier and hydrocarbon, just thereby the PSA device can play the function of selector switch will be divided into from the synthetic gas of partial combustion device and be rich in the CO logistics and be rich in H
2Logistics: be rich in the CO logistics and be admitted to power generation process and be rich in H
2Logistics then is sent to the hydrocarbon synthesis process.The principle of operation of pressure conversion absorption and hydrocarbon synthesis all belongs to known content thereby need not to give unnecessary details.Main application scenario is a power large-scale electric generating station.The hydrogen that exists in the synthetic gas by the coal generation is used to the hydrocarbon of high additive level.The power generation capacity of residual gas is influenced hardly even increase arranged slightly.
With such as adopting traditional CO conversion process to compare as the structure of connecting rod, this structure more effectively, more cheap.
As shown in the figure, structure of the present invention is composed as follows:
A) in coal gasification apparatus 1, produce the synthetic gas that lacks hydrogen,
B) at pressure conversion adsorption unit 2(PSA) in, the carbon monoxide in most of coal synthetic gas is adsorbed, and the hydrogen logistics is rich in generation.This rich hydrogenous logistics merges formation through pipeline 3 and part coal synthetic gas and possesses required H
2The heavy paraffin hydrocarbon of/CO ratio synthesizes (HPS) gas.Carbon monoxide is by desorb and be imported into internal combustion turbine 4 and generate electricity; And
C) in synthesizer 5, synthetic as required, isomerization and fractionation alkane.
Import coal and use through pipeline A such as containing the 95%(mole through what pipeline B provided by the cryogenic air separation plant (not shown)) pressurized stream the pure oxygen in coal gasifier 1 with its gasification.For instance, the coal input speed is about 4000 tons/day, and vapor pressure is 25 crust, and temperature is suitable for making coal to produce high thermal efficiency.
Synthetic gas is removed a large amount of solids through suitable process (not shown).This can finish by the dry method that adopts an above cyclonic separator or other device.After this, stripping acid gas components (great majority are hydrogen sulfide) wherein removes the carbonic acid gas and the water that produce in residual solid and some process simultaneously.This process in a series of washing tower, absorption tower and flashing tower by adopting a part of physics or chemical absorber such as Sulfinol or Selexol to carry out.Exhaust flow leads to the removal process (not shown) that is used to collect sulphur.
The H of the gas that process purifies
2/ CO ratio is 0.25-0.70, and temperature is 40 ℃, and pressure is 20 crust.
Embodiment
With 4000 tons of/day gasifications, form 8 * 10 with oxygen
6Standard cubic meter (NM
3) day synthetic gas, wherein H
2/ CO ratio is about 0.25-0.70.Synthetic gas has removed particle, HCN and H through handling
2S.
The suitable practice is to transform and CO at CO-
2Remove and handle 20-30% coal synthetic gas in the device 6 so that produce about 1 * 10
6Nm
3Satisfy the town gas 6a of CO and calorific value specification.Remainder is sent to PSA device 2.
The 60-70% synthetic gas that produces in the coal gasification apparatus is divided into two logistics in PSA device 2:
-be used for the rich CO logistics (H of power generation process 4,4a
2/ CO is about 0.14-0.06),
-Fu H
2Logistics (H
2/ CO is about 10.5-4.5), it and remaining 15-5% coal synthetic gas merge becomes H
2/ CO ratio is synthetic (HPS) gas of heavy paraffin hydrocarbon of 2.1.
Can be by pressure conversion absorption (PSA) the hydrogenation post-processing step of a small amount of feed hydrogen of further purifying for use in product.
Synthetic gas at first is converted into a series of straight chain hydrocarbon 5a by heavy paraffin hydrocarbon synthetic (HPS).
After this, with straight-chain paraffin and the hydrocarbon stream overall separation of scope,, remove the alkene and the oxygenation material (Oxygenates) that are used for alkane solvent and washing composition charging through after the hydrotreatment at C5-17.
To be converted into lightweight oil, kerosene and gas oil in remaining straight chain hydrocarbon logistics feeding heavy paraffin hydrocarbon conversion (HPC) device.
The thermo-efficiency of whole technological process is about 48-50%.Compare with the corresponding associated enterprises that adopts traditional carbon monoxide conversion process, this technology not only possesses the advantage of less investment, and can produce higher thermo-efficiency.
The visual particular case of step that produces town gas decides what to use, and should not be considered essential feature of the present invention.
For the professional of this area, it is evident that and to carry out various improvement by foregoing and accompanying drawing to the present invention.These improve and belong to scope of the present invention equally.
Claims (4)
1, a kind of method of utilizing the preparing hydrocarbon from synthetic gas that is produced by coal, it comprises the following steps:
A) partial combustion subdivided solids carbonaceous fuel and oxygen-containing gas;
B) handle described synthetic gas so that remove particle, HCN and H
2S;
C) synthetic gas that at least a portion is prepared in step a) adds in the hydrocarbon synthesis unit;
D) synthetic gas that makes in step a) has H
2/ CO is than being 0.25-0.70;
E) with at least a portion synthetic gas that makes in the step a), add in the pressure conversion absorption unit, wherein most of CO is adsorbed H in the hydrogen-rich stream that is produced
2The scope of/CO ratio is 3-15;
F) synthetic gas that is produced by the partial combustion process in step c) by the hydrogen-rich stream that will make in step e) and part merges the hydrogen richness with the raw material of regulating feed-in hydrocarbon synthesizer mutually, makes this be used for the raw material H of hydrocarbon synthesizer
2The scope of/CO ratio is 1-3
G) make the CO desorb of adsorbing in the step e), thereby obtain wherein H
2/ CO is the rich CO logistics of 0.05-0.25 than scope,
It is characterized in that:
With the CO of this desorb raw material as power generation assembly; And wherein
H) generating is the exit at power generation assembly, and the hydrocarbon sintetics is to make in the exit of hydrocarbon synthesis unit.
2, the method for claim 1 is characterized in that from step a) and b) a part of synthetic gas transform and CO at CO one
2Remove in the device and handle, to form town gas, the remainder of wherein said synthetic gas is by feed-in pressure conversion absorption unit.
3, the method for claim 2 is characterized in that transforming and CO at CO one
2Remove and handle 20-30% coal synthetic gas in the device.
4, the method for claim 3 is characterized in that synthetic gas that 60-70% produces is at pressure conversion adsorption unit 2(PSA in coal gasification apparatus) in be divided into two bursts of logistics; The rich CO logistics (H that is used to generate electricity
2/ CO is than for about 0.14-0.06) and can with remain 15-5% coal synthetic gas and be merged into and be heavy hydrocarbon synthesis (HPS) gas (H
2/ CO ratio is 2: 1) hydrogen-rich stream (H
2/ CO ratio is about 10.5-4.5).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8925476A GB2237814A (en) | 1989-11-10 | 1989-11-10 | A method and apparatus for co-generating power and hydrocarbons from coal derived synthesis gas using pressure swing absorption |
| GB8925476.7 | 1989-11-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1051619A CN1051619A (en) | 1991-05-22 |
| CN1026149C true CN1026149C (en) | 1994-10-05 |
Family
ID=10666109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90108965A Expired - Fee Related CN1026149C (en) | 1989-11-10 | 1990-11-08 | Method and apparatus for co-generating power and hydrocarbons from coal derived synthesis gas using pressure swing absorption |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1026149C (en) |
| GB (1) | GB2237814A (en) |
| ZA (1) | ZA908960B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162373A (en) * | 1995-10-03 | 2000-12-19 | Exxon Research And Engineering Company | Removal of hydrogen cyanide from synthesis gas (Law322) |
| CN1211534A (en) * | 1997-06-09 | 1999-03-24 | 大同北产株式会社 | Gas generator and method for generating gas by using same |
| US7500997B2 (en) * | 2002-02-05 | 2009-03-10 | The Regents Of The University Of California | Steam pyrolysis as a process to enhance the hydro-gasification of carbonaceous materials |
| CN1733873B (en) * | 2004-08-11 | 2010-05-26 | 日本气体合成株式会社 | Method for producing liquefied petroleum gas |
| WO2008099313A2 (en) | 2007-02-12 | 2008-08-21 | Sasol Technology (Proprietary) Limited | Co-production of power and hydrocarbons |
| CN101663376B (en) * | 2007-02-12 | 2013-06-12 | 沙索技术有限公司 | Co-production of power and hydrocarbons |
| US7909913B2 (en) | 2008-07-17 | 2011-03-22 | Air Products And Chemicals, Inc. | Gas purification by adsorption of hydrogen sulfide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2165551B (en) * | 1984-10-10 | 1988-08-17 | Shell Int Research | Process for the production of synthesis gas |
-
1989
- 1989-11-10 GB GB8925476A patent/GB2237814A/en not_active Withdrawn
-
1990
- 1990-11-08 ZA ZA908960A patent/ZA908960B/en unknown
- 1990-11-08 CN CN90108965A patent/CN1026149C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB2237814A (en) | 1991-05-15 |
| GB8925476D0 (en) | 1989-12-28 |
| CN1051619A (en) | 1991-05-22 |
| ZA908960B (en) | 1991-08-28 |
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Granted publication date: 19941005 Termination date: 20091208 |