CN111979000A - Coal water slurry prepared from benzene extraction residual liquid and preparation method thereof - Google Patents
Coal water slurry prepared from benzene extraction residual liquid and preparation method thereof Download PDFInfo
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- CN111979000A CN111979000A CN201910437324.4A CN201910437324A CN111979000A CN 111979000 A CN111979000 A CN 111979000A CN 201910437324 A CN201910437324 A CN 201910437324A CN 111979000 A CN111979000 A CN 111979000A
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- benzene extraction
- water slurry
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- extraction raffinate
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 239000003245 coal Substances 0.000 title claims abstract description 147
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002002 slurry Substances 0.000 title claims abstract description 81
- 238000000605 extraction Methods 0.000 title claims abstract description 76
- 239000007788 liquid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000002309 gasification Methods 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002802 bituminous coal Substances 0.000 claims abstract description 30
- 239000003250 coal slurry Substances 0.000 claims abstract description 29
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003830 anthracite Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 239000010865 sewage Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 235000019738 Limestone Nutrition 0.000 claims description 8
- 239000006028 limestone Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- WWBXZKQQXUFSED-UHFFFAOYSA-N [Na].O=C.C1=CC=C2C(S(=O)(=O)OC)=CC=CC2=C1 Chemical compound [Na].O=C.C1=CC=C2C(S(=O)(=O)OC)=CC=CC2=C1 WWBXZKQQXUFSED-UHFFFAOYSA-N 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 claims description 2
- HLPHHOLZSKWDAK-UHFFFAOYSA-M sodium;formaldehyde;naphthalene-1-sulfonate Chemical compound [Na+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HLPHHOLZSKWDAK-UHFFFAOYSA-M 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 239000013505 freshwater Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000036284 oxygen consumption Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000002956 ash Substances 0.000 description 38
- 239000002893 slag Substances 0.000 description 21
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 18
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 230000002354 daily effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000009798 Shen-Fu Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/324—Dispersions containing coal, oil and water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
- C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses coal water slurry prepared by using benzene extraction raffinate and a preparation method thereof, wherein the coal water slurry comprises the following components in parts by weight: 600-800 parts of blended coal; 150-400 parts of benzene extraction raffinate; 0.1-10 parts of an additive; the blended coal comprises bituminous coal and anthracite, and the weight ratio of the bituminous coal to the anthracite is 5: 1-1: 5. The method uses the benzene extraction waste liquid to replace fresh water, adopts the mixing of anthracite and bituminous coal, and the prepared water-coal slurry has no corrosion to a rod mill, has good slurrying performance and high ash melting point, adopts a water-cooled wall gasifier to gasify the water-coal slurry, has high gasification reaction temperature, low oxygen consumption and high carbon conversion rate, has low COD content of gasification sewage and sewage discharge amount discharged by the gasifier, and improves the coal adaptability while realizing the resource utilization of the benzene extraction residual liquid.
Description
Technical Field
The invention relates to coal water slurry prepared from benzene extraction raffinate and a preparation method thereof, belonging to the technical field of petrochemical industry.
Background
Caprolactam is an important organic chemical raw material. The cyclohexanone ammoximation method is mainly adopted in China to produce caprolactam. The beckmann rearrangement process unit of the cyclohexanone ammoximation process produces a large amount of benzene extraction raffinate. The benzene extraction raffinate is a light red transparent liquid, has slight smell, has the characteristics of strong acidity (pH value of 3-6), large yield, complex composition (wherein the content of ammonium sulfate is 5-7%, the content of caprolactam is 0.2-1.0%), high COD content (50-150 g/L) and the like, and is a typical organic waste liquid with high concentration which is difficult to treat. Taking a set of caprolactam production device with 30 ten thousand tons per year as an example, the yield of benzene extraction raffinate is 600-700 tons per day.
The caprolactam industry usually uses a concentration burning method and a concentration extraction method to treat benzene extraction raffinate. Wherein the more successful benzene extraction raffinate treatment process is a concentration incineration method. CN1281826A discloses a method for treating benzene extraction waste liquid in caprolactam production. The method firstly uses alkaline liquor to neutralize benzene extraction raffinate to be neutral, then concentrates and dehydrates, and then sends the concentrated solution to an incinerator for treatment. The method has the advantages of good treatment effect and the disadvantages of high treatment cost and serious corrosion of the incinerator due to the fact that a large amount of steam is needed in the evaporation process and auxiliary fuel is needed in the incineration. The treatment cost of each ton of benzene extraction raffinate is about 160-200 yuan.
CN105836949A discloses a method for treating benzene extraction raffinate in caprolactam production. The method comprises the steps of firstly concentrating and dehydrating benzene extraction raffinate by using low-pressure steam, then adding benzene, mixing, standing and layering to obtain a benzene layer containing caprolactam, an organic waste liquid layer and an ammonium sulfate-containing water layer. The method has the advantages of simple process and the disadvantages that a large amount of steam is needed in the evaporation process, and an organic waste liquid layer needs to be further treated by a subsequent unit.
In a word, the caprolactam industry does not have a low-cost, simple and reliable resource benzene extraction raffinate treatment process at present.
From 1990, the coal water slurry gasification technology is rapidly developed and successfully developed. For example, CN105505471A discloses a coal water slurry gasification process method suitable for treating high-concentration ammonia nitrogen and COD sewage. Grinding a mixture of bituminous coal, wastewater and an additive in a ball mill to prepare coal water slurry, pressurizing the coal water slurry by using a high-pressure coal slurry pump, feeding the mixture into a coal water slurry gasification furnace to perform incomplete oxidation reaction with pure oxygen, wherein organic matters in the wastewater and organic matters in the coal undergo incomplete oxidation reaction at the gasification temperature of 1300-1400 ℃ and the gasification pressure of 2-3 MPag to generate high-pressure raw coal gas, and the main gas components of the raw coal gas are carbon monoxide, hydrogen, methane and carbon dioxide. The method has the advantages that the method can treat high-concentration organic waste liquid (the COD content is 100000mg/L), and has the defects that the gasification reaction temperature is relatively low, the COD content in gasification sewage discharged by a gasification furnace is 800-1300 mg/L, the discharge amount of the waste water is large, and the further treatment of a sewage treatment plant is required.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the coal water slurry prepared by using the benzene extraction residual liquid and the preparation method thereof, the benzene extraction waste liquid is used for replacing fresh water, anthracite and bituminous coal are mixed, the prepared coal water slurry has no corrosion to a rod mill, the slurry forming property is good, the ash melting point is high, a water-cooled wall gasifier is used for gasifying the coal water slurry, the gasification reaction temperature is high, the oxygen consumption is low, the carbon conversion rate is high, the COD content of gasification sewage and the sewage discharge amount discharged by the gasifier are low, and the coal adaptability is improved while the resource utilization of the benzene extraction residual liquid is realized.
In the present invention, Aad represents an air-drying base ash, Mad represents air-drying base moisture, i.e., internal water, and ad represents an air-drying base.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the coal water slurry prepared from the benzene extraction raffinate comprises the following components in parts by weight:
600-800 parts of mixed coal;
150-400 parts of benzene extraction raffinate;
0.1-10 parts of an additive;
the blended coal comprises bituminous coal and anthracite, and the weight ratio of the bituminous coal to the anthracite is 5: 1-1: 5.
The slurry-forming property of the coal-water slurry is generally related to the properties of coal and water, and compared with fresh water, the slurry-forming property of the coal-water slurry is poor when the same coal is used due to the fact that the waste water contains some inorganic salts, and particularly when the same coal slurry viscosity (<1200 mPa-s) is achieved, the dry-basis concentration of the coal-water slurry prepared by the waste water is 1 to 2 percent lower than that of the coal-water slurry prepared by the fresh water.
The internal water content of the coal has a greater impact on the slurry-forming properties of the coal-water slurry when the same amount of fresh water or wastewater is used. Generally, qualified coal water slurry can be prepared only by requiring the content of Mad in internal water of coal to be less than 6 percent, namely, the viscosity to be less than 1200mPa & s, the concentration of dry coal slurry to be 60.1 to 70.0 percent and the ash content to be Aad 8 to 20 percent.
The coal water slurry gasification industry generally uses the bituminous coal of Shenfu coal field to prepare the coal water slurry, and the characteristics of the bituminous coal are as follows: (1) the Mad of the internal water is high and fluctuates between 4 and 10 percent, which causes the fluctuation of the dry basis concentration of the coal water slurry prepared by bituminous coal to be about 60.1 percent, the coal water slurry with qualified slurry performance can not be reliably prepared, but the ash content can be ensured to be qualified; (2) ash Aad low (< 8%): when the waste water is used for replacing fresh water and Shenfu coal field bituminous coal to prepare the coal water slurry, the dry basis concentration of the coal slurry is further reduced, and the gasification economic benefit is reduced.
The anthracite has the characteristics that: (1) internal water Mad is low (< 2%); (2) the ash content Aad is higher and fluctuates between 20 percent and 28 percent, so the coal water slurry with qualified slurry forming performance but unqualified ash content can be reliably prepared by using the anthracite.
The invention mixes the anthracite and the bituminous coal strictly according to the required proportion, and can prepare the coal water slurry with qualified slurry forming performance and ash content through the synergistic effect of the components.
Preferably, the components further comprise a fluxing agent, the fluxing agent is limestone powder with a medium diameter of 5-50 um, and the addition amount of the fluxing agent is as follows: the weight of the limestone powder/the weight of the obtained base mixed coal is not higher than 0.03. The ash melting point of anthracite is usually more than 1500 ℃, the ash melting point of bituminous coal is usually 1180-1380 ℃, limestone is used as a fluxing agent, and the limestone can be reasonably added according to the components of the mixed coal in the actual process to reduce the ash melting point of the mixed coal.
Preferably, in the blended coal, the weight ratio of bituminous coal to anthracite is 2: 1-1: 1.
Preferably, the ash content Aad of the blended coal is 8-20%, the ash melting point is 1300-1450 ℃, and the internal water Mad is not higher than 6%.
Preferably, the benzene extraction raffinate is alkalescent and is obtained by mixing and reacting the benzene extraction raffinate and an alkaline solution, and the pH value of the benzene extraction raffinate is 7.0-7.9.
The additive is at least one selected from sodium naphthalene sulfonate formaldehyde condensate, sodium methyl naphthalene sulfonate formaldehyde condensate, sodium dibutyl naphthalene sulfonate formaldehyde condensate, sodium lignosulfonate, potassium lignosulfonate and calcium lignosulfonate. The small amount of additive can reduce the surface tension of water and raise the surface tension of coal powder, so that polar water and non-polar coal powder can permeate mutually to form stable suspension.
Preferably, the concentration of the dry coal slurry of the coal water slurry is 60.1-70.0%, the viscosity is less than 1200mPa & s, and the ash content is Aad 8-20%.
Preferably, the coal water slurry is sent to a water-cooled wall gasification furnace, the gasification temperature is 1450-1600 ℃, the gasification pressure is 3.0-7.0MPag, the gasification reaction occurs, the COD removal rate of the benzene extraction residual liquid is 98.0-99.9%, the carbon conversion rate in the mixed coal is 97.0-99.5%, and the COD content of gasification sewage discharged by the gasification furnace is 100-500 mg/L.
More preferably, the high-pressure coal slurry pump feeds the coal slurry into a coal slurry channel of the three-channel burner, and high-pressure oxygen respectively enters a central oxygen channel and an outer oxygen channel of the burner; the method comprises the steps of enabling coal water slurry in a nozzle of a burner to collide with oxygen, uniformly mixing and atomizing the coal water slurry, enabling the coal water slurry to enter a water-cooled wall gasifier, enabling gasification reaction to generate high-pressure high-temperature crude gas under the environment of the gasification temperature of 1450-1600 ℃ and the gasification pressure of 3.0-7.0MPag, enabling pollutants in benzene extraction raffinate to be decomposed into carbon monoxide and carbon dioxide, enabling the COD removal rate of the benzene extraction raffinate to be 98.0-99.9%, the carbon conversion rate in mixed coal to be 97.0-99.5%, and enabling the COD content of gasification sewage discharged from the gasifier to be 100-500 mg/L.
The gasification furnaces are classified into: refractory brick gasification furnaces and water-cooled wall gasification furnaces.
The ash content Aad of the coal as fired used in the firebrick gasifier is required to be less than 12% (under the high temperature condition of the gasifier, the ash content in the coal has erosion effect on the fire-facing surface of the firebrick, the higher the ash content is, the higher the erosion effect is, the limit of the ash content Aad of the coal as fired is needed), the ash melting point is required to be less than 1300 ℃ (the high temperature in the gasifier has great influence on the service life of the firebrick, the higher the reaction temperature is, the shorter the service life of the firebrick is, the upper limit of the reaction temperature is required to be limited, and the reaction temperature is equal to the melting point of the coal as fired +50 ℃, so the upper limit of the reaction temperature is indirectly limited by limiting the upper limit.
The ash content Aad of the blended coal is 8-20%, and the ash melting point is 1300-1450 ℃. These 2 indexes contradict with the coal index for a firebrick gasifier, so that a firebrick gasifier cannot be used, and only a water-cooled wall gasifier can be used. The water-cooled wall gasifier adopts the principle of slag resistance to protect the water-cooled wall, has requirements (> 8%) on the lower limit of the ash content Aad of the coal as fired and has no requirements on the upper limit of the ash content Aad of the coal as fired. Therefore, the upper limit of ash content of the coal as fired is defined as an economic requirement. The higher the ash content of the coal as fired, the poorer the gasification economy.
The reaction temperature of the water-cooled wall gasifier is equal to the melting point of the added coal ash plus 150 ℃. Therefore, the gasification reaction temperature can reach 1450-1600 ℃. While the reaction temperature of the firebrick gasifier is less than 1350 ℃. That is, the reaction temperature of the water-cooled wall gasifier is 200-250 ℃ higher than that of the refractory brick gasifier. The coal gasification reaction is a non-catalytic reaction, the reaction pressure, the reactant concentration and the reaction activation energy are relatively stable, the influence of the reaction pressure, the reactant concentration and the reaction activation energy on the gasification reaction speed can be ignored, but the influence of the reaction temperature on the gasification reaction speed is obvious, the gasification reaction speed is higher as the reaction temperature is higher, and the carbon conversion rate and the COD removal rate in the benzene extraction residual liquid are favorably improved. As shown in Table 1, the operating parameters and results for the refractory brick gasification process and the water wall gasification process are compared:
table 1 comparison of operating parameters and results of two gasification processes
The invention also provides a preparation method of the coal water slurry, which comprises the following steps:
(1) preparation of blended coal
Mixing bituminous coal and anthracite coal uniformly according to a set weight ratio;
(2) benzene extraction raffinate pretreatment
Mixing and reacting the benzene extraction residual liquid with an alkaline solution to prepare weakly alkaline benzene extraction residual liquid, wherein the pH value of the weakly alkaline benzene extraction residual liquid is 7.0-7.9, and gaseous ammonia generated by the reaction is sent to an ammonia torch for incineration;
(3) Preparation of coal water slurry
And mixing the blended coal, the weakly alkaline benzene extraction raffinate, the fluxing agent and the additive according to a set proportion, and grinding the mixture uniformly in a rod mill to obtain the coal water slurry.
Compared with the prior art, the invention has the following beneficial effects:
1. the coal water slurry prepared from the benzene extraction residual liquid and pure oxygen are subjected to gasification reaction in a gasification furnace at high temperature and high pressure, and pollution factors such as organic matters in the benzene extraction residual liquid are converted into carbon monoxide, carbon dioxide and hydrogen to be used as raw materials for producing synthetic ammonia, so that the resource utilization of the benzene extraction residual liquid is realized. The operation cost of treating the benzene extraction residual liquid by a concentration burning method is greatly saved;
2. the fresh water resource required by the coal water slurry is saved;
3. because the water-cooled wall gasifier is adopted to gasify the coal water slurry prepared from the benzene extraction raffinate, the gasification reaction temperature is 1450-1600 ℃, the carbon conversion rate is high, the COD content of the gasification sewage discharged by the gasifier is reduced to 100-500 mg/L, and the discharge amount of the gasification sewage is reduced;
4. because the anthracite and the bituminous coal are adopted to prepare the blended coal, the dry basis concentration of the coal water slurry can be improved to 60.1-70.0%;
5. because the anthracite and the bituminous coal are used for preparing the blended coal, and a proper proportion of fluxing agent is added, the ash melting point of the coal as fired can be increased to 1300-1450 ℃, the gasification reaction temperature can be increased to 1450-1600 ℃, the carbon conversion rate is increased, and the high oxygen consumption is avoided;
6. Because the blended coal is prepared from the anthracite and the bituminous coal, the ash content Aad of the coal as fired can be improved to 8-20%, so that a slag layer is favorably formed on the inner surface of the water-cooled wall of the gasification furnace, slag is resisted, and the water-cooled wall is protected;
7. because the anthracite and the bituminous coal are adopted to prepare the blended coal, the adaptability of the coal type is favorably improved;
8. because a water vapor system consisting of a water-cooled wall and a steam pocket is adopted, high-pressure saturated steam can be produced as a byproduct, and the energy utilization efficiency is favorably improved;
9. after benzene extraction raffinate is neutralized to alkalescence, corrosion of a rod mill can be avoided.
Drawings
FIG. 1 is a schematic view of a gasification process in a coal water slurry gasification process according to example 1 of the present invention;
wherein: 1-a low pressure neutralization tank; 2-rod mill; 3-a coal slurry tank; 4-high pressure coal slurry pump; 5-a coal water slurry burner; 6-water coal slurry water-cooled wall gasification furnace; 7-water-cooled wall; 8-high pressure steam drum; 9-weak alkaline benzene extraction raffinate conveying pipeline; 10-low pressure coal water slurry pipeline; 11-high pressure water coal slurry pipeline; 12-boiler feed water piping; 13-saturation furnace water downcomer; 14-a steam-water mixture riser; 15-a high-pressure oxygen pipeline for removing the central oxygen channel of the burner; 16-a high-pressure oxygen pipeline for removing the external oxygen channel of the burner; 17-high pressure saturated steam pipeline.
FIG. 2 is a flow chart of the blended coal preparation of the present invention;
wherein: 21-a coal blending unit; 22-a first flat belt; 23-a second flat belt; 24-third flat belt.
Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto.
The inventor tests the performance of the coal water slurry obtained by different mixed coals, and the result is shown in the table 2:
TABLE 2 Water-coal slurry Property parameter Table obtained from different blended coals
As shown in fig. 1 to 2, the concrete embodiment of applying the coal water slurry prepared by using the benzene extraction raffinate to the gasification process of the present invention comprises the following steps:
1) preparation of blended coal
The first flat belt 22 for the smokeless coal and the second flat belt 23 for the bituminous coal are fed into the coal blending device 21 in a certain proportion to prepare blended coal, and then the blended coal is fed into the rod mill 2 by the third flat belt 24. The coal blending device is provided with a belt scale, a PLC control system and an impeller type coal feeder with adjustable rotating speed. The weight mixing proportion of the bituminous coal and the anthracite is adjusted through a PLC (programmable logic controller), and the mixed coal with the ash content of Aad 8-20%, the ash melting point of 1300-1450 ℃ and the internal water Mad of less than 6% is prepared.
The selected bituminous coal is Shenyou No. 2 bituminous coal with low ash content and low ash melting point produced by Shenhua company. The anthracite is produced by Shanxi Luan group company and has high ash content and high ash melting point. The ratio of the bituminous coal to the anthracite coal is selected to be 5: 1-1: 5. The rotating speed of the impeller type coal feeder is adjusted through a PLC of the coal blending device, so that the weight blending proportion of bituminous coal and anthracite can be stably controlled to be 5: 1-1: 5.
The production capacity of the blending device is 2000-4000 tons of finished blended coal per day.
2) Benzene extraction raffinate pretreatment
And (3) carrying out neutralization reaction on the benzene extraction raffinate and an alkaline solution in a low-pressure neutralization tank 1, and controlling the pH value of the benzene extraction raffinate at 7.0-7.9 to prepare the weakly alkaline benzene extraction raffinate. The low-pressure gaseous ammonia generated by neutralization is sent to an ammonia torch for incineration. The low-pressure neutralization tank is provided with a reaction pressure control system, and the reaction pressure is controlled to be 30-50 KPag.
The alkaline solution can be a sodium hydroxide solution with the mass concentration of 5-10%, alkaline waste water discharged by an ion exchange resin regeneration unit, or saponified waste alkali liquor.
3) Preparation of coal water slurry
The mixture of the blended coal, the weakly alkaline benzene extraction raffinate, the fluxing agent and the coal water slurry additive is ground in a rod mill 2 to prepare the coal water slurry with qualified slurry property, and then the coal water slurry is sent into a coal slurry tank 3 through a low-pressure coal slurry pipeline 10, and then the high-pressure coal water slurry is sent to a coal water slurry burner 5 of a water-cooled wall gasifier 6 through a high-pressure coal slurry pump 4 through a high-pressure coal slurry pipeline 11. The ash melting point of the mixed coal is controlled between 1300 ℃ and 1450 ℃ by adjusting the adding proportion of the fluxing agent, so that the problem of high oxygen consumption of the coal water slurry prepared from the benzene extraction residual liquid during gasification is solved.
The fluxing agent is dry limestone powder with a median diameter of 5-50 um. The fluxing agent is metered and added directly to the blended coal in the third flat belt 24.
4) Gasification of coal water slurry
The water-coal-slurry burner 5 is arranged at the top of the water-cooled wall gasification furnace 6. The burner 5 is provided with a central oxygen passage, an outer oxygen passage and an inner water-coal-slurry passage. The high-pressure coal slurry pump 4 sends the coal slurry into the coal slurry channel of the burner 5, and high-pressure oxygen from the boundary area respectively enters the central oxygen channel and the outer oxygen channel of the burner 5 through the high- pressure oxygen pipelines 15 and 16. The coal water slurry in the nozzle collides with oxygen, is uniformly mixed and atomized, then enters a water-cooled wall gasifier 6, is subjected to gasification reaction at the gasification temperature of 1450-1600 ℃ and under the gasification pressure of 3.0-7.0MPag to generate high-pressure and high-temperature crude gas, and pollutants in the benzene extraction residual liquid are almost completely decomposed into carbon monoxide and carbon dioxide.
And melting ash in the coal water slurry at the high temperature of 1450-1600 ℃ in the gasifier, and forming a slag layer on the inner surface of the water-cooled wall under the action of a backflow effect in the hearth. The slag layer is divided into a fixed slag layer and a flowing slag layer.
When the total slag layer is thin, the interior of the liquid slag layer is gradually cooled to the ash melting point for solidification, and the fixed slag layer and the total slag layer are thickened; when the total slag layer is thicker, the thermal resistance of the slag layer is increased, the heat transfer is slowed down, the temperature of the flowing slag layer is increased, the fluidity is improved, the thickness of the liquid slag layer is reduced, and the dynamic balance of the thickness of the slag layer is formed. When the ash content and ash composition of coal entering a furnace are stable, the oxygen-coal ratio is controlled stably, and the working condition of a water vapor system in a water-cooled wall is stable, the gasification temperature is kept relatively stable, so that the fluidity of slag and the thickness of a slag layer are kept relatively stable in a dynamic state, the slag is resisted by slag, and the water-cooled wall is protected from hydrogen corrosion and sulfur corrosion of synthesis gas, high-temperature ablation and slag abrasion.
The high-pressure high-temperature raw gas enters a raw gas chilling system of the water-cooled wall gasifier 6 downwards for cooling.
The inside of the water wall gasification furnace 6 is provided with a water wall 7. A steam pocket 8 is arranged outside the water-cooled wall gasification furnace 6 (at the highest point of the gasification frame). The steam drum 8 and the water-cooled wall 7 form a natural convection water vapor system.
High pressure boiler feed water from the battery limits enters the drum 8 through a boiler feed water line 12. Saturated furnace water at the lower part of the steam pocket 8 enters the lower part of the water-cooled wall 7 through a saturated furnace water downcomer 13, after being heated, part of the saturated furnace water is vaporized to generate a steam-water mixture, and the steam-water mixture is circulated back to the middle part of the steam pocket through a steam-water mixture riser 14 to separate out saturated steam. Saturated steam generated at the upper part of the steam drum 8 is sent into a medium-pressure steam pipe network through a high-pressure saturated steam pipeline 17.
The water vapor system can take out heat released by gasification reaction in the form of high-pressure saturated steam, so that the reaction heat balance is maintained, and the water-cooled wall is not damaged.
The operation data of the water-cooled wall coal water slurry gasification device for daily treatment of 600 tons of benzene extraction residual liquid are as follows:
1. the processing capacity of the coal water slurry gasification furnace is as follows: 600 tons of benzene extraction raffinate (COD content 100g/L) is treated daily; 1410 tons of mixed coal (as received) are added daily, wherein 470 tons of shanxi Lu' an anthracite and 940 tons of Shenyou No. 2 bituminous coal are added; 14.1 tons of limestone powder is thrown in the day; 2.6 tons of coal slurry additive are added every day; Pure oxygen consumption of 37000NM3/h。
2. Effective gas production capacity of the coal water slurry gasification furnace: effective gas (CO + H)2) The yield was 85000NM3The effective gas pressure is 4.0Mpag, and the temperature of an effective gas outlet area is 195-205 ℃; the concentration of CO in the raw gas is 45 percent and the CO content in the raw gas is 45 percent2Concentration 20% H2Concentration 35% CH4The concentration was 1000 ppm.
3. Saturated steam production capacity of the coal water slurry gasification furnace: the yield was 2.2t/h and the saturation vapour pressure was 5.5 Mpag.
4. 0.687t/KNM of raw coal with effective gas consumption3(CO+H2) Effective gas consumption dry base raw coal 0.618t/KNM3(CO+H2) Effective gas oxygen consumption 435NM3/KNM3(CO+H2)。
5. The COD content of the gasified sewage discharged by the gasifier is 500 mg/L; the flow rate was 32 t/h.
6. The COD removal rate of the benzene extraction raffinate was 99.3%.
7. The carbon conversion rate in the mixed coal was 97.6%.
8. The concentration of the coal water slurry prepared from the benzene extraction residual liquid is 61.5 percent.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple variations, equivalent substitutions or modifications based on the present invention to achieve substantially the same technical effects are within the scope of the present invention.
Claims (10)
1. A coal water slurry prepared by using benzene extraction raffinate is characterized in that: the paint comprises the following components in parts by weight:
600-800 parts of mixed coal;
150-400 parts of benzene extraction raffinate;
0.1-10 parts of an additive;
the blended coal comprises bituminous coal and anthracite, and the weight ratio of the bituminous coal to the anthracite is 5: 1-1: 5.
2. The coal water slurry prepared by using the benzene extraction raffinate as claimed in claim 1, wherein: the components further comprise a fluxing agent, the fluxing agent is limestone powder with a median diameter of 5-50 um, and the addition amount of the fluxing agent is as follows: the weight of the limestone powder/the weight of the obtained base mixed coal is not higher than 0.03.
3. The coal water slurry prepared by using the benzene extraction raffinate as claimed in claim 1, wherein: in the mixed coal, the weight ratio of bituminous coal to anthracite is 2: 1-1: 1.
4. The coal water slurry prepared by using the benzene extraction raffinate as claimed in claim 1, wherein: the ash content Aad of the blended coal is 8-20%, the ash melting point is 1300-1450 ℃, and the internal water Mad is not higher than 6%.
5. The coal water slurry prepared by using the benzene extraction raffinate as claimed in claim 1, wherein: the benzene extraction raffinate is alkalescent and is obtained by mixing and reacting the benzene extraction raffinate with an alkaline solution, and the pH value of the benzene extraction raffinate is 7.0-7.9.
6. The coal water slurry prepared by using the benzene extraction raffinate as claimed in claim 1, wherein: the additive is at least one selected from sodium naphthalene sulfonate formaldehyde condensate, sodium methyl naphthalene sulfonate formaldehyde condensate, sodium dibutyl naphthalene sulfonate formaldehyde condensate, sodium lignosulfonate, potassium lignosulfonate and calcium lignosulfonate.
7. The coal water slurry prepared by using the benzene extraction raffinate as claimed in claim 1, wherein: the concentration of the coal water slurry dry-based coal slurry is 60.1-70.0%, the viscosity is less than 1200mPa & s, and the ash content is Aad 8-20%.
8. The coal water slurry prepared by using the benzene extraction raffinate as claimed in claim 1, wherein: the coal water slurry is sent to a water-cooled wall gasification furnace, the gasification temperature is 1450-1600 ℃, the gasification pressure is 3.0-7.0MPag, the gasification reaction occurs, the COD removal rate of the benzene extraction residual liquid is 98.0-99.9%, the carbon conversion rate in the mixed coal is 97.0-99.5%, and the COD content of gasification sewage discharged by the gasification furnace is 100-500 mg/L.
9. The coal water slurry prepared by using the benzene extraction raffinate according to claim 8, wherein: the high-pressure coal slurry pump feeds the coal slurry into a coal slurry channel of the three-channel burner, and high-pressure oxygen respectively enters a central oxygen channel and an outer oxygen channel of the burner; the method comprises the steps of enabling coal water slurry in a nozzle of a burner to collide with oxygen, uniformly mixing and atomizing the coal water slurry, enabling the coal water slurry to enter a water-cooled wall gasifier, enabling gasification reaction to generate high-pressure high-temperature crude gas under the environment of the gasification temperature of 1450-1600 ℃ and the gasification pressure of 3.0-7.0MPag, enabling pollutants in benzene extraction raffinate to be decomposed into carbon monoxide and carbon dioxide, enabling the COD removal rate of the benzene extraction raffinate to be 98.0-99.9%, the carbon conversion rate in mixed coal to be 97.0-99.5%, and enabling the COD content of gasification sewage discharged from the gasifier to be 100-500 mg/L.
10. The process for the preparation of a coal water slurry according to any one of claims 1 to 9, comprising the steps of:
(1) preparation of blended coal
Mixing bituminous coal and anthracite coal uniformly according to a set weight ratio;
(2) benzene extraction raffinate pretreatment
Mixing and reacting the benzene extraction residual liquid with an alkaline solution to prepare weakly alkaline benzene extraction residual liquid, wherein the pH value of the weakly alkaline benzene extraction residual liquid is 7.0-7.9, and gaseous ammonia generated by the reaction is sent to an ammonia torch for incineration;
(3) preparation of coal water slurry
And mixing the blended coal, the weakly alkaline benzene extraction raffinate, the fluxing agent and the additive according to a set proportion, and grinding the mixture uniformly in a rod mill to obtain the coal water slurry.
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