CN104004557B - Crushed coal pressure gasifying associating coal water slurry gasification produces the method for coal preparing natural gas - Google Patents
Crushed coal pressure gasifying associating coal water slurry gasification produces the method for coal preparing natural gas Download PDFInfo
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Abstract
The invention discloses the method that crushed coal pressure gasifying associating coal water slurry gasification produces coal preparing natural gas, effectively can solve the fast smalls equilibrium problem and high-concentration phenolic wastewater problem that exist in crushed coal pressure gasifying explained hereafter coal preparing natural gas process.Crushed coal pressurized-gasification furnace adopts block coal as raw material, and coal slurry gasifier and the last coal as raw material of project assorted boiler, solve the block smalls equilibrium problem in supporting colliery.The waste water that crushed coal pressure gasifying produces is after membrane sepn, fresh water reuse, dense water is as coal water slurry gasification slurrying water, utilize the high-temperature gasification process of coal slurry gasifier, organic pollutant gasification in dense water is decomposed, reluctant crushed coal pressure gasifying process spent water is converted into more tractable coal water slurry gasification sewage, greatly reduces cost of sewage disposal.
Description
Technical field
The invention belongs to derived energy chemical and sewage treatment area, relate to crushed coal pressure gasifying associating coal water slurry gasification and produce coal preparing natural gas, be specifically related to block smalls equilibrium problem and crushed coal pressure gasifying process spent water process problem in gasified raw material.
Background technology
Adopt crushed coal pressure gasifying explained hereafter coal preparing natural gas to have the advantage that efficiency is high, byproduct is many, but itself there is block smalls balance and produce high-concentration phenolic wastewater two difficult problems in crushed coal pressure gasifying technology.First crushed coal pressure gasifying technique belongs to fixed bed gasification, requires that feed coal is the lump coal of 6 ~ 50mm.Along with improving constantly of coal mining mechanization degree, in feed coal, smalls content is relatively many, crushed coal pressure gasifying technique is adopted to there is lump coal and smalls equilibrium problem, newly-built coal preparing natural gas project, polygamy cover large coal mine, lump coal, smalls consumption is unbalance, bring very large smalls selling pressure can to supporting colliery.Secondly in the waste water that produces of crushed coal pressure gasifying containing organic compound such as a large amount of tar, middle oil, phenols, complicated component, intractability much larger than dry coal powder gasification and coal water slurry gasification sewage, therefore sewage treatment facility investment and running cost relatively high.
CN102649683 proposes the method with the strange gasification waste water in water-coal slurry furnace process Shandong, but the method is directly used in preparation coal water slurry by after strange for Shandong gasification waste water sedimentation ash disposal,, phenol, ammonia coal-tar middle oil for waste water do not reclaim, affect economic benefit, a large amount of existence of tar in addition, affect the stability of coal water slurry, easily cause demixing phenomenon.
Summary of the invention
The object of this invention is to provide the method that a kind of crushed coal pressure gasifying associating coal water slurry gasification produces coal preparing natural gas, the block smalls equilibrium problem simultaneously solving supporting colliery contains phenol processing wastewater problem with the high density in production.
For achieving the above object, the technical solution used in the present invention is as follows:
Crushed coal pressure gasifying associating coal water slurry gasification of the present invention produces the method for coal preparing natural gas, it is characterized in that, comprises the following steps:
(1) raw coal is after fragmentation, screening, be divided into the lump coal of particle diameter 6 ~ 50mm and the smalls of particle diameter <6mm, the lump coal of particle diameter 6 ~ 50mm delivers to crushed coal pressure gasifying device by endless belt conveyor, and the smalls of particle diameter <6mm delivers to coal water slurry gasifying device by endless belt conveyor;
(2) gas liquor that crushed coal pressure gasifying device and conversion refrigerating unit are sent here reclaims tar, phenol ammonia recovery unit recovery crude phenols and ammonia through gas liquor tripping device, then be separated by membrane separation unit, remove phenols wherein and ammonia, produce fresh water and carry out reuse, dense water is sent to coal water slurry gasifying device and prepares coal water slurry, and fresh water does circulating cooling make-up water or the moisturizing of coal water slurry gasification ash water system;
(3) the dense water mixer mill that the smalls of particle diameter <6mm and membrane separation unit are sent here makes coal water slurry, coal water slurry is pumped into coal slurry gasifier through high-pressure coal slurry and gasifies, and the organism such as the phenols in dense water gasify decomposition in high-temperature gasification environment;
(4) coal water slurry gasification raw gas is after cooling, mix with the cooled crushed coal pressure gasifying raw gas of conversion, send into low temperature washing device for methanol, remove coal gas medium sulphide content, unnecessary carbonic acid gas and other impurity to obtain synthesizing, synthetic gas enters methane synthesis device, and methanation reaction occurs, and reaction generates the synthetic natural gas that methane content is not less than 95%, send into TEG dehydration device after compression, after removing moisture, obtain coal preparing natural gas.
Concrete technology is as follows:
(1) raw coal is after fragmentation, screening, be divided into the lump coal of particle diameter 6 ~ 50mm and the smalls of particle diameter <6mm, the lump coal of particle diameter 6 ~ 50mm delivers to crushed coal pressure gasifying device by endless belt conveyor, and the smalls of particle diameter <6mm delivers to coal water slurry gasifying device by endless belt conveyor;
(2) particle diameter is that the lump coal of 6 ~ 50mm gasifies in crushed coal pressurized-gasification furnace, and vaporized chemical is middle pressure steam and oxygen, and the volume ratio of middle pressure steam and oxygen is 6 ~ 8:1; Leave 180 DEG C of vapourizing furnace, 3.8MPa raw gas is with CO, H
2, CH
4, H
2o and CO
2for main ingredient;
(3) crushed coal pressure gasifying raw gas sends into sulfur-resisting transformation device, and adopt cobalt-molybdenum catalyst, temperature of reaction is between 200 ~ 450 DEG C.There is transformationreation:
CO+H
2O→H
2+CO
2
Reaction to carbon monoxide in gas mixture and hydrogen volume ratio meets H
2/ (CO+CO
2)=3.1 ~ 3.3;
(4) gas liquor that crushed coal pressure gasifying device and conversion refrigerating unit are sent here enters gas liquor tripping device, and reclaim tar, middle oil through oil separator, oil-in-water content is less than 1000mg/L, by sending into phenol ammonia recovery unit after two medium filter;
(5) gas liquor enters phenol ammonia recovery unit, removes most ammonia through stripping, then after methyl iso-butyl ketone (MIBK) extraction removes most of phenols and other organism, sends process spent water;
(6) crushed coal pressure gasifying process spent water is after sand filtration and secondary filter, send into membrane separation unit, obtain the dense water of 40% and the fresh water of 60%, dense water is sent to coal water slurry gasifying device and prepares coal water slurry, fresh water does coal water slurry gasification ash water system make up water, prevents ash water system chlorion from exceeding standard;
(7) smalls of particle diameter <6mm is sent to coal water slurry gasifying device, and the dense water mixer mill that membrane separation unit is sent here makes the coal water slurry that concentration is 55 ~ 62%; Coal water slurry is pumped into coal slurry gasifier through high-pressure coal slurry and gasifies, and generates CO, H
2, CO
2, and a small amount of CH
4, H
2s gas;
(8), after coal water slurry gasification raw gas is cooled to 40 DEG C, mixes with the cooled crushed coal pressure gasifying raw gas of conversion, send into low temperature washing device for methanol, remove coal gas medium sulphide content, unnecessary carbonic acid gas and other impurity, go out CO in the synthetic gas of low-temperature rectisol
2<1.5%, total sulfur <0.1ppm;
(9) synthetic gas going out low temperature washing device for methanol enters methane synthesis device, adopts nickel-base catalyst, and temperature of reaction, between 320 ~ 620 DEG C, methanation reaction occurs:
CO+3H
2→CH
4+H
2O
CO
2+4H
2→CH
4+2H
2O
Reaction generates the synthetic natural gas that methane content is not less than 95%, sends into TEG dehydration device after compression, obtains coal preparing natural gas after removing moisture.
Being separated by membrane separation unit described in step (2), its concrete technology is:
(1) first remove mechanical impurity through mechanical filter and secondary filter from the gas liquor of phenol ammonia recovery unit discharge, prevent from resulting in blockage to film or damaging;
(2) gas liquor after filtering adds alkali adjust ph to 9 ~ 10.5, makes the phenols in gas liquor form phenol negative oxygen ion, prevents from causing dirty blocking up to film, then removes most phenols and other organism in sewage by membrane separation unit;
(3) fresh water that step (2) is discharged adds acid for adjusting pH to 6 ~ 8, makes free ammonia form ammonium salt, is removed the most ammonia nitrogens in sewage by final stage film.
In the present invention, crushed coal pressurized-gasification furnace adopts block coal as raw material, and last coal as raw material then used by coal slurry gasifier and project assorted boiler, solves the block smalls equilibrium problem in supporting colliery.Waste water, after phenol ammonia recovery unit reclaims most of tar, middle oil, crude phenols and ammonia, is then separated to level Four membranous system by three, removes phenols wherein and ammonia, produce fresh water and carry out reuse, dense water is for the preparation of coal water slurry.Utilize the high-temperature gasification process of coal slurry gasifier, organic pollutant gasification in dense water is decomposed, by reluctant crushed coal pressure gasifying process spent water (COD3000 ~ 4500mg/L, phenols 600 ~ 1000mg/L, ammonia nitrogen 200 ~ 300mg/L) be converted into more tractable coal water slurry gasification sewage (COD500mg/L, ammonia nitrogen 200 ~ 300mg/L, substantially not containing phenols), greatly reduce sewage disposal difficulty and cost.
Method of the present invention effectively can solve the fast smalls equilibrium problem and high-concentration phenolic wastewater problem that exist in crushed coal pressure gasifying explained hereafter coal preparing natural gas process.Crushed coal pressurized-gasification furnace adopts block coal as raw material, and coal slurry gasifier and the last coal as raw material of project assorted boiler, solve the block smalls equilibrium problem in supporting colliery.The waste water that crushed coal pressure gasifying produces is after membrane sepn, fresh water reuse, dense water is as coal water slurry gasification slurrying water, utilize the high-temperature gasification process of coal slurry gasifier, organic pollutant gasification in dense water is decomposed, reluctant crushed coal pressure gasifying process spent water is converted into more tractable coal water slurry gasification sewage, greatly reduces cost of sewage disposal.
Accompanying drawing explanation
fig. 1 is process flow sheet of the present invention.
Embodiment
embodiment 1
As shown in Figure 1, crushed coal pressure gasifying associating coal water slurry gasification of the present invention produces the method for coal preparing natural gas, and concrete technology step is as follows:
1, raw coal is after fragmentation, screening, is divided into 6 ~ 50mm lump coal and <6mm smalls, delivers to crushed coal pressure gasifying device, coal water slurry gasifying device and boiler respectively by endless belt conveyor.
2,6 ~ 50mm lump coal gasifies in crushed coal pressurized-gasification furnace, and vaporized chemical is middle pressure steam and oxygen, and the volume ratio of middle pressure steam and oxygen is 6 ~ 8:1.Leave 180 DEG C of vapourizing furnace, 3.8MPa raw gas is with CO, H
2, CH
4, H
2o and CO
2for main ingredient, also have CnHm, N
2, sulfide, tar, petroleum naphtha, the impurity such as phenols and ammonia.
3, crushed coal pressure gasifying raw gas sends into sulfur-resisting transformation device, adopts cobalt-molybdenum catalyst, and temperature of reaction, between 200 ~ 450 DEG C, transformationreation occurs:
CO+H
2O→H
2+CO
2
Methane synthesis H is met to adjust carbon monoxide and hydrogen ratio in raw gas
2/ (CO+CO
2the requirement of)=3.1 ~ 3.3.Reclaim reaction heat, coal gas is cooled to 40 DEG C and sends into low temperature washing device for methanol.
4, the gas liquor that crushed coal pressure gasifying device and conversion refrigerating unit are sent here enters gas liquor tripping device, and reclaim tar, middle oil through oil separator, oil-in-water content is less than 1000mg/L, by sending into phenol ammonia recovery unit after two medium filter.
5, gas liquor enters phenol ammonia recovery unit, most ammonia is removed through stripping, again after methyl iso-butyl ketone (MIBK) extraction removes most of phenols and other organism, send process spent water, in process spent water, COD is about 3000 ~ 4500mg/L, phenols is about 600 ~ 1000mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
6, crushed coal pressure gasifying process spent water is after sand filtration and secondary filter, sends into reverse osmosis unit, obtains the dense water of 40% and the fresh water of 60%.In dense water, COD is about 8500 ~ 11000mg/L, and phenols is about 1500 ~ 2500mg/L, and ammonia nitrogen is about 600-800mg/L.In fresh water, COD is about 40mg/L, and ammonia nitrogen is about 5mg/L.Dense water is sent to coal water slurry gasifying device and prepares coal water slurry, and fresh water does coal water slurry gasification ash water system make up water, prevents ash water system chlorion from exceeding standard.
7, <6mm smalls is sent to coal water slurry gasifying device, and the dense water mixer mill that membrane separation unit is sent here makes the coal water slurry that concentration is 55 ~ 62%.Coal water slurry is pumped into coal slurry gasifier through high-pressure coal slurry and gasifies, and generates CO, H
2, CO
2, and a small amount of CH
4, H
2the gases such as S.
8, pulp water separation is carried out at ash water system in coal water slurry gasification Heisui River, and buck major part recycles, and be the chlorion in control buck and salts contg, small part buck is sent to waste water biochemical treatment device.In the buck sent, COD is about 500mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
9, after coal water slurry gasification raw gas is cooled to 40 DEG C, mixes with the cooled crushed coal pressure gasifying raw gas of conversion, send into low temperature washing device for methanol, remove coal gas medium sulphide content, unnecessary carbonic acid gas and other impurity.Go out CO in the synthetic gas of low-temperature rectisol
2<1.5%, total sulfur <0.1ppm.
10, the synthetic gas going out low temperature washing device for methanol enters methane synthesis device, and methanation reaction occurs, and adopt nickel-base catalyst, temperature of reaction is between 320 ~ 620 DEG C:
CO+3H
2→CH
4+H
2O
CO
2+4H
2→CH
4+2H
2O
Reaction generates the synthetic natural gas that methane content is not less than 95%, sends into TEG dehydration device after compression, enters gas distributing system after removing moisture.
embodiment 2
As shown in the figure, crushed coal pressure gasifying associating coal water slurry gasification of the present invention produces the method for coal preparing natural gas, and concrete technology step is as follows:
1, raw coal is after fragmentation, screening, is divided into 6 ~ 50mm lump coal and <6mm smalls, delivers to crushed coal pressure gasifying device, coal water slurry gasifying device and boiler respectively by endless belt conveyor.
2,6 ~ 50mm lump coal gasifies in crushed coal pressurized-gasification furnace, and vaporized chemical is middle pressure steam and oxygen, and the volume ratio of middle pressure steam and oxygen is 6:1.Leave 180 DEG C of vapourizing furnace, 3.8MPa raw gas is with CO, H
2, CH
4, H
2o and CO
2for main ingredient, also have CnHm, N
2, sulfide, tar, petroleum naphtha, the impurity such as phenols and ammonia.
3, crushed coal pressure gasifying raw gas sends into sulfur-resisting transformation device, adopts cobalt-molybdenum catalyst, and temperature of reaction, between 200 ~ 220 DEG C, transformationreation occurs:
CO+H
2O→H
2+CO
2
Methane synthesis H is met to adjust carbon monoxide and hydrogen ratio in raw gas
2/ (CO+CO
2the requirement of)=3.1 ~ 3.3.Reclaim reaction heat, coal gas is cooled to 40 DEG C and sends into low temperature washing device for methanol.
4, the gas liquor that crushed coal pressure gasifying device and conversion refrigerating unit are sent here enters gas liquor tripping device, and reclaim tar, middle oil through oil separator, oil-in-water content is less than 1000mg/L, by sending into phenol ammonia recovery unit after two medium filter.
5, gas liquor enters phenol ammonia recovery unit, most ammonia is removed through stripping, again after methyl iso-butyl ketone (MIBK) extraction removes most of phenols and other organism, send process spent water, in process spent water, COD is about 3000 ~ 4500mg/L, phenols is about 600 ~ 1000mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
6, crushed coal pressure gasifying process spent water is after sand filtration and secondary filter, sends into reverse osmosis unit, obtains the dense water of 40% and the fresh water of 60%.In dense water, COD is about 8500 ~ 11000mg/L, and phenols is about 1500 ~ 2500mg/L, and ammonia nitrogen is about 600-800mg/L.In fresh water, COD is about 40mg/L, and ammonia nitrogen is about 5mg/L.Dense water is sent to coal water slurry gasifying device and prepares coal water slurry, and fresh water does coal water slurry gasification ash water system make up water, prevents ash water system chlorion from exceeding standard.
7, <6mm smalls is sent to coal water slurry gasifying device, and the dense water mixer mill that membrane separation unit is sent here makes the coal water slurry that concentration is 55 ~ 62%.Coal water slurry is pumped into coal slurry gasifier through high-pressure coal slurry and gasifies, and generates CO, H
2, CO
2, and a small amount of CH
4, H
2the gases such as S.
8, pulp water separation is carried out at ash water system in coal water slurry gasification Heisui River, and buck major part recycles, and be the chlorion in control buck and salts contg, small part buck is sent to waste water biochemical treatment device.In the buck sent, COD is about 500mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
9, after coal water slurry gasification raw gas is cooled to 40 DEG C, mixes with the cooled crushed coal pressure gasifying raw gas of conversion, send into low temperature washing device for methanol, remove coal gas medium sulphide content, unnecessary carbonic acid gas and other impurity.Go out CO in the synthetic gas of low-temperature rectisol
2<1.5%, total sulfur <0.1ppm.
10, the synthetic gas going out low temperature washing device for methanol enters methane synthesis device, and methanation reaction occurs, and adopt nickel-base catalyst, temperature of reaction is between 320 ~ 360 DEG C:
CO+3H
2→CH
4+H
2O
CO
2+4H
2→CH
4+2H
2O
Reaction generates the synthetic natural gas that methane content is not less than 95%, sends into TEG dehydration device after compression, enters gas distributing system after removing moisture.
embodiment 3
As shown in Figure 1, crushed coal pressure gasifying associating coal water slurry gasification of the present invention produces the method for coal preparing natural gas, and concrete technology step is as follows:
1, raw coal is after fragmentation, screening, is divided into 6 ~ 50mm lump coal and <6mm smalls, delivers to crushed coal pressure gasifying device, coal water slurry gasifying device and boiler respectively by endless belt conveyor.
2,6 ~ 50mm lump coal gasifies in crushed coal pressurized-gasification furnace, and vaporized chemical is middle pressure steam and oxygen, and the volume ratio of middle pressure steam and oxygen is 7:1.Leave 180 DEG C of vapourizing furnace, 3.8MPa raw gas is with CO, H
2, CH
4, H
2o and CO
2for main ingredient, also have CnHm, N
2, sulfide, tar, petroleum naphtha, the impurity such as phenols and ammonia.
3, crushed coal pressure gasifying raw gas sends into sulfur-resisting transformation device, adopts cobalt-molybdenum catalyst, and temperature of reaction, between 300 ~ 320 DEG C, transformationreation occurs:
CO+H
2O→H
2+CO
2
Methane synthesis H is met to adjust carbon monoxide and hydrogen ratio in raw gas
2/ (CO+CO
2the requirement of)=3.1 ~ 3.3.Reclaim reaction heat, coal gas is cooled to 40 DEG C and sends into low temperature washing device for methanol.
4, the gas liquor that crushed coal pressure gasifying device and conversion refrigerating unit are sent here enters gas liquor tripping device, and reclaim tar, middle oil through oil separator, oil-in-water content is less than 1000mg/L, by sending into phenol ammonia recovery unit after two medium filter.
5, gas liquor enters phenol ammonia recovery unit, most ammonia is removed through stripping, again after methyl iso-butyl ketone (MIBK) extraction removes most of phenols and other organism, send process spent water, in process spent water, COD is about 3000 ~ 4500mg/L, phenols is about 600 ~ 1000mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
6, crushed coal pressure gasifying process spent water is after sand filtration and secondary filter, sends into reverse osmosis unit, obtains the dense water of 40% and the fresh water of 60%.In dense water, COD is about 8500 ~ 11000mg/L, and phenols is about 1500 ~ 2500mg/L, and ammonia nitrogen is about 600-800mg/L.In fresh water, COD is about 40mg/L, and ammonia nitrogen is about 5mg/L.Dense water is sent to coal water slurry gasifying device and prepares coal water slurry, and fresh water does coal water slurry gasification ash water system make up water, prevents ash water system chlorion from exceeding standard.
7, <6mm smalls is sent to coal water slurry gasifying device, and the dense water mixer mill that membrane separation unit is sent here makes the coal water slurry that concentration is 55 ~ 62%.Coal water slurry is pumped into coal slurry gasifier through high-pressure coal slurry and gasifies, and generates CO, H
2, CO
2, and a small amount of CH
4, H
2the gases such as S.
8, pulp water separation is carried out at ash water system in coal water slurry gasification Heisui River, and buck major part recycles, and be the chlorion in control buck and salts contg, small part buck is sent to waste water biochemical treatment device.In the buck sent, COD is about 500mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
9, after coal water slurry gasification raw gas is cooled to 40 DEG C, mixes with the cooled crushed coal pressure gasifying raw gas of conversion, send into low temperature washing device for methanol, remove coal gas medium sulphide content, unnecessary carbonic acid gas and other impurity.Go out CO in the synthetic gas of low-temperature rectisol
2<1.5%, total sulfur <0.1ppm.
10, the synthetic gas going out low temperature washing device for methanol enters methane synthesis device, and methanation reaction occurs, and adopt nickel-base catalyst, temperature of reaction is between 480 ~ 500 DEG C:
CO+3H
2→CH
4+H
2O
CO
2+4H
2→CH
4+2H
2O
Reaction generates the synthetic natural gas that methane content is not less than 95%, sends into TEG dehydration device after compression, enters gas distributing system after removing moisture.
embodiment 4
As shown in Figure 1, crushed coal pressure gasifying associating coal water slurry gasification of the present invention produces the method for coal preparing natural gas, and concrete technology step is as follows:
1, raw coal is after fragmentation, screening, is divided into 6 ~ 50mm lump coal and <6mm smalls, delivers to crushed coal pressure gasifying device, coal water slurry gasifying device and boiler respectively by endless belt conveyor.
2,6 ~ 50mm lump coal gasifies in crushed coal pressurized-gasification furnace, and vaporized chemical is middle pressure steam and oxygen, and the volume ratio of middle pressure steam and oxygen is 8:1.Leave 180 DEG C of vapourizing furnace, 3.8MPa raw gas is with CO, H
2, CH
4, H
2o and CO
2for main ingredient, also have CnHm, N
2, sulfide, tar, petroleum naphtha, the impurity such as phenols and ammonia.
3, crushed coal pressure gasifying raw gas sends into sulfur-resisting transformation device, adopts cobalt-molybdenum catalyst, and temperature of reaction, between 440 ~ 450 DEG C, transformationreation occurs:
CO+H
2O→H
2+CO
2
Methane synthesis H is met to adjust carbon monoxide and hydrogen ratio in raw gas
2/ (CO+CO
2the requirement of)=3.1 ~ 3.3.Reclaim reaction heat, coal gas is cooled to 40 DEG C and sends into low temperature washing device for methanol.
4, the gas liquor that crushed coal pressure gasifying device and conversion refrigerating unit are sent here enters gas liquor tripping device, and reclaim tar, middle oil through oil separator, oil-in-water content is less than 1000mg/L, by sending into phenol ammonia recovery unit after two medium filter.
5, gas liquor enters phenol ammonia recovery unit, most ammonia is removed through stripping, again after methyl iso-butyl ketone (MIBK) extraction removes most of phenols and other organism, send process spent water, in process spent water, COD is about 3000 ~ 4500mg/L, phenols is about 600 ~ 1000mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
6, crushed coal pressure gasifying process spent water is after sand filtration and secondary filter, sends into reverse osmosis unit, obtains the dense water of 40% and the fresh water of 60%.In dense water, COD is about 8500 ~ 11000mg/L, and phenols is about 1500 ~ 2500mg/L, and ammonia nitrogen is about 600-800mg/L.In fresh water, COD is about 40mg/L, and ammonia nitrogen is about 5mg/L.Dense water is sent to coal water slurry gasifying device and prepares coal water slurry, and fresh water does coal water slurry gasification ash water system make up water, prevents ash water system chlorion from exceeding standard.
7, <6mm smalls is sent to coal water slurry gasifying device, and the dense water mixer mill that membrane separation unit is sent here makes the coal water slurry that concentration is 55 ~ 62%.Coal water slurry is pumped into coal slurry gasifier through high-pressure coal slurry and gasifies, and generates CO, H
2, CO
2, and a small amount of CH
4, H
2the gases such as S.
8, pulp water separation is carried out at ash water system in coal water slurry gasification Heisui River, and buck major part recycles, and be the chlorion in control buck and salts contg, small part buck is sent to waste water biochemical treatment device.In the buck sent, COD is about 500mg/L, and ammonia nitrogen is about 200 ~ 300mg/L.
9, after coal water slurry gasification raw gas is cooled to 40 DEG C, mixes with the cooled crushed coal pressure gasifying raw gas of conversion, send into low temperature washing device for methanol, remove coal gas medium sulphide content, unnecessary carbonic acid gas and other impurity.Go out CO in the synthetic gas of low-temperature rectisol
2<1.5%, total sulfur <0.1ppm.
10, the synthetic gas going out low temperature washing device for methanol enters methane synthesis device, and methanation reaction occurs, and adopt nickel-base catalyst, temperature of reaction is between 600 ~ 620 DEG C:
CO+3H
2→CH
4+H
2O
CO
2+4H
2→CH
4+2H
2O
Reaction generates the synthetic natural gas that methane content is not less than 95%, sends into TEG dehydration device after compression, enters gas distributing system after removing moisture.
Claims (2)
1. crushed coal pressure gasifying associating coal water slurry gasification produces a method for coal preparing natural gas, and it is characterized in that, concrete technology is as follows:
(1) raw coal is after fragmentation, screening, be divided into the lump coal of particle diameter 6 ~ 50mm and the smalls of particle diameter <6mm, the lump coal of particle diameter 6 ~ 50mm delivers to crushed coal pressure gasifying device by endless belt conveyor, and the smalls of particle diameter <6mm delivers to coal water slurry gasifying device by endless belt conveyor;
(2) particle diameter is that the lump coal of 6 ~ 50mm gasifies in crushed coal pressurized-gasification furnace, and vaporized chemical is middle pressure steam and oxygen, and the volume ratio of middle pressure steam and oxygen is 6 ~ 8:1; Leave 180 DEG C of vapourizing furnace, 3.8MPa raw gas is with CO, H
2, CH
4, H
2o and CO
2for main ingredient;
(3) crushed coal pressure gasifying raw gas sends into sulfur-resisting transformation device, and adopt cobalt-molybdenum catalyst, temperature of reaction is between 200 ~ 450 DEG C; There is transformationreation:
CO+H
2O→H
2+CO
2
Reaction to carbon monoxide in gas mixture and hydrogen volume ratio meets H
2/ (CO+CO
2)=3.1 ~ 3.3;
(4) gas liquor that crushed coal pressure gasifying device and conversion refrigerating unit are sent here enters gas liquor tripping device, and reclaim tar, middle oil through oil separator, oil-in-water content is less than 1000mg/L, by sending into phenol ammonia recovery unit after two medium filter;
(5) gas liquor enters phenol ammonia recovery unit, and phenol ammonia recovery unit reclaims crude phenols and ammonia, removes most ammonia through stripping, then after methyl iso-butyl ketone (MIBK) extraction removes most of phenols and other organism, sends process spent water;
(6) crushed coal pressure gasifying process spent water is after sand filtration and secondary filter, send into membrane separation unit, remove phenols wherein and ammonia, obtain the dense water of 40% and the fresh water of 60%, dense water is sent to coal water slurry gasifying device and prepares coal water slurry, fresh water does coal water slurry gasification ash water system make up water, prevents ash water system chlorion from exceeding standard;
(7) smalls of particle diameter <6mm is sent to coal water slurry gasifying device, and the dense water mixer mill that membrane separation unit is sent here makes the coal water slurry that concentration is 55 ~ 62%; Coal water slurry is pumped into coal slurry gasifier through high-pressure coal slurry and gasifies, and the phenol organic matter in dense water gasifies decomposition in high-temperature gasification environment; Generate CO, H
2, CO
2, and a small amount of CH
4, H
2s gas;
(8), after coal water slurry gasification raw gas is cooled to 40 DEG C, mixes with the cooled crushed coal pressure gasifying raw gas of conversion, send into low temperature washing device for methanol, remove coal gas medium sulphide content, unnecessary carbonic acid gas and other impurity, go out CO in the synthetic gas of low-temperature rectisol
2<1.5%, total sulfur <0.1ppm;
(9) synthetic gas going out low temperature washing device for methanol enters methane synthesis device, adopts nickel-base catalyst, and temperature of reaction, between 320 ~ 620 DEG C, methanation reaction occurs:
CO+3H
2→CH
4+H
2O
CO
2+4H
2→CH
4+2H
2O
Reaction generates the synthetic natural gas that methane content is not less than 95%, sends into TEG dehydration device after compression, obtains coal preparing natural gas after removing moisture.
2. crushed coal pressure gasifying associating coal water slurry gasification according to claim 1 produces the method for coal preparing natural gas, and it is characterized in that, being separated by membrane separation unit described in step (2), its concrete technology is:
(1) first remove mechanical impurity through mechanical filter and secondary filter from the gas liquor of phenol ammonia recovery unit discharge, prevent from resulting in blockage to film or damaging;
(2) gas liquor after filtering adds alkali adjust ph to 9 ~ 10.5, makes the phenols in gas liquor form phenol negative oxygen ion, prevents from causing dirty blocking up to film, then removes most phenols and other organism in sewage by membrane separation unit;
(3) fresh water that step (2) is discharged adds acid for adjusting pH to 6 ~ 8, makes free ammonia form ammonium salt, is removed the most ammonia nitrogens in sewage by final stage film.
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|---|---|---|---|
| CN201410078063.9A CN104004557B (en) | 2014-03-05 | 2014-03-05 | Crushed coal pressure gasifying associating coal water slurry gasification produces the method for coal preparing natural gas |
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| CN109111954B (en) * | 2018-09-26 | 2020-11-17 | 泗县田原秸秆回收再利用有限责任公司 | High-efficiency coal gas preparation method |
| CN109536225A (en) * | 2019-01-16 | 2019-03-29 | 西安科技大学 | A kind of gasification system and method applied near coal-mine natural gas from coal |
| CN111718760B (en) * | 2020-06-23 | 2021-03-02 | 中国华能集团清洁能源技术研究院有限公司 | Sulfur-tolerant methanation system and method for coal-based natural gas |
| CN112852491B (en) * | 2020-12-11 | 2021-11-12 | 中科合成油技术有限公司 | Method and system for obtaining coal-based synthetic oil and co-producing LNG (liquefied Natural gas) by double-head gasification |
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