CN109762585A - A method of with waste water water-coal-slurry and passing through water-coal-slurry preparing ethylene glycol - Google Patents
A method of with waste water water-coal-slurry and passing through water-coal-slurry preparing ethylene glycol Download PDFInfo
- Publication number
- CN109762585A CN109762585A CN201910093099.7A CN201910093099A CN109762585A CN 109762585 A CN109762585 A CN 109762585A CN 201910093099 A CN201910093099 A CN 201910093099A CN 109762585 A CN109762585 A CN 109762585A
- Authority
- CN
- China
- Prior art keywords
- coal
- water
- slurry
- gas
- ethylene glycol
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 210
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000003250 coal slurry Substances 0.000 title claims abstract description 140
- 239000002351 wastewater Substances 0.000 title claims abstract description 69
- 239000003245 coal Substances 0.000 claims abstract description 225
- 230000008569 process Effects 0.000 claims abstract description 150
- 239000007789 gas Substances 0.000 claims abstract description 137
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000002309 gasification Methods 0.000 claims abstract description 92
- 238000001035 drying Methods 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000002817 coal dust Substances 0.000 claims abstract description 64
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000428 dust Substances 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- -1 nitrous acid ester Chemical class 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 230000006315 carbonylation Effects 0.000 claims description 10
- 238000005810 carbonylation reaction Methods 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical class ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 7
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 description 35
- 239000003921 oil Substances 0.000 description 26
- 235000019198 oils Nutrition 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000011280 coal tar Substances 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003034 coal gas Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 235000019476 oil-water mixture Nutrition 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000032258 transport Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003901 oxalic acid esters Chemical class 0.000 description 2
- 238000006709 oxidative esterification reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The present invention provides a kind of with waste water water-coal-slurry and passes through the method for water-coal-slurry preparing ethylene glycol, and low-order coal handles the low-order coal after being dried and exhaust gas by stoving process, and exhaust gas obtains the first coal dust through dedusting；Low-order coal after drying is handled to obtain gas mixture by the reducing process that gasifies, gasification reducing process is the chemical reaction process for heating the low-order coal after drying under anaerobic or micro-oxygen conditions；By gas mixture according to through dedusting and oil gas cooling treatment to the first waste water；Water-coal-slurry includes the first waste water, the first coal dust and slurries additive agent, coal water slurry gasification is obtained water-gas, water-gas passes sequentially through purification, shift conversion handles to obtain synthesis gas；Synthesis gas separating-purifying is respectively obtained into CO and H2；With CO and H2Ethylene glycol is prepared using oxalate method for raw material, waste utilization economizes on resources, and solves the problems, such as that existing low order moisture in coal recycling is insufficient and pollutes environment, and low in cost, has huge market prospects.
Description
Technical field
The present invention relates to coal substance clean utilization technical field more particularly to it is a kind of with waste water water-coal-slurry and pass through water coal
The method for starching preparing ethylene glycol.
Background technique
More than half is low-order coal in the explored coal reserves in China, wherein the volatile matter contained is equivalent to 100,000,000,000
The petroleum resources of ton.Low-order coal mainly has the substance characteristics of high-moisture, high volatile, and in burning, flame is longer and has cigarette,
Degree of coalification is lower, and typical coal is lignite and jet coal.The few oily deficency of China's richness coal, becomes how to efficiently use low-order coal and works as
The key subjects of modern clean coal technology.However either combustion power generation or Modern Coal-based Chemical utilize, all because of its Gao Shui, height
The efficiency that three big characteristics of ash and low heat value comprehensively utilize it is extremely low.
Ethylene glycol is widely used in production polyester, anti-icing fluid, surface-active as a kind of important Organic Chemicals
The products such as agent, lubricant, plasticizer, cosmetics.With the rapid development of China's polyester industrial, need of the domestic market to ethylene glycol
The amount of asking sustainable growth.Although ethylene glycol production capacity in China's is increased every year on average with 10% or so speed in recent years, mesh
Preceding country's ethylene glycol yield is far from ever-increasing market demand is met, and external dependence degree is always above 60%.Therefore, how
Ethylene glycol production capacity is improved to solve domestic ethylene glycol imbalance between supply and demand, it has also become the major issue of the sector urgent need to resolve.
Drying is that low-order coal is former as boiler oil, gasified raw material, direct liquefaction raw material, pyrolysis feed or other deep processings
The first step of material.Drying is both the needs for meeting downstream processing requirement, and reduces entire project energy consumption and downstream unit
The needs of investment.What is generated in drying process is directly discharged into atmosphere comprising exhaust gas such as a large amount of vapor and coal dust etc., can aggravate
Environmental pollution, therefore the coal dust of the generation effectively in recycling drying process and moisture have important practical significance.In low-order coal
Moisture be generally divided into Free water and combine water, and it is dry be typically only capable to remove most Free water in low-order coal, be very difficult to
Except the combination water in low-order coal, most of Free water that usual drying process drying is removed is easy the recycling that is condensed.But
The Efficient Conversion Land use systems of usual low-order coal is are pyrolyzed after drying, still containing a large amount of in the high-temperature gas after pyrolysis
The content of vapor, this part water also should not be underestimated.However, it is contemplated that water content is higher in low-order coal, and low order is produced in richness
The regional water of coal is often of great rarity；If can be effectively recycled in water resource and drying course valuable in ground low-order coal simultaneously
Pulverized coal preparation water-coal-slurry, the chemical products ethylene glycol of water-coal-slurry preparation high value is recycled, not only to solving existing low-order coal
Middle moisture recycling is insufficient and pollution environment has great importance, and can synthesize the high ethylene glycol of added value.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of with waste water water-coal-slurry and leads to
The method for crossing water-coal-slurry preparing ethylene glycol effectively recycles the coal dust generated in moisture and drying course in low-order coal for making
Water-coal-slurry, recycles coal water slurry gasification to prepare the unstripped gas of synthesizing glycol, and waste utilization economizes on resources, solves existing low
The problem of recycling of rank moisture in coal is insufficient and pollution environment, and be that raw material prepares ethylene glycol with waste water etc., low in cost, reaction
Mild condition has huge market prospects.
In order to solve the above technical problems, the present invention provides the following technical scheme that
A method of with waste water water-coal-slurry and by water-coal-slurry preparing ethylene glycol, method includes the following steps:
(1) low-order coal handles the low-order coal after being dried and exhaust gas by stoving process, and the exhaust gas is through the first dedusting
Technique obtains the first coal dust；
(2) low-order coal after drying described in step (1) is handled to obtain gas mixture by the reducing process that gasifies, institute
Stating gasification reducing process is the chemical reaction process heated under anaerobic or micro-oxygen conditions to the low-order coal after drying；
(3) gas mixture described in step (2) is passed sequentially through into the second dust collecting process and oil gas cooling technique is handled, obtained
To the first waste water；
(4) water-coal-slurry includes the first waste water described in step (3), the first coal dust and water-coal-slurry described in step (1)
Additive, by the water-coal-slurry and O2It handles to obtain comprising CO, CO by coal-water slurry gasification2And H2Water-gas, the water
Coal gas passes sequentially through purification process and shift conversion process obtains synthesis gas；
(5) CO and H are respectively obtained after handling synthesis gas described in step (4) by process for separating and purifying2；The CO with
Nitrous acid ester by carbonylation coupling process synthesis of diethyl oxalate employing, the diethy-aceto oxalate again with the H2Hydrogenation reaction is carried out to obtain
To thick ethylene glycol, the thick ethylene glycol obtains the ethylene glycol after passing through Purification Catalysts of Monoethylene Glycol.
Water-coal-slurry is a kind of environmental clean fuel of New type coal base flow body, burning of coal characteristic has both been remained, but also with class
It is the real clean coal technology in one, current China like the liquid-phase combustion application characteristic of heavy oil.Water-coal-slurry by 65-70% coal,
The water of 29-34% and chemical addition agent less than 1%, are made by certain processing technology, appearance picture oil, good fluidity,
Convenient transportation, high combustion efficiency, pollutant (SO2、NOX) discharge it is low, about 2t water-coal-slurry can substitute 1t fuel oil, can be in industrial pot
The generation oil such as furnace, station boiler and Industrial Stoves or coal, gas use；Water-coal-slurry crosses coal-water slurry gasification preparation CO and H2, it is system
The indispensable conversion gas of standby ethylene glycol etc..
Slurries additive agent mainly includes viscosity reduction dispersing agent and stabilizer.Wherein dispersing agent is mostly important, it is directly affected
The quality and preparation cost of water-coal-slurry.(1) dispersing agent: the surface of coal has strong hydrophobicity, cannot be intimately associated with water
As a kind of slurry, a kind of wet walk only will form in higher concentration.A small amount of dispersing agent is added in slurrying and changes coal
The surface nature of grain, making coal particle surface tightly is that additive molecule and hydration shell surround, and coal grain is allowed to be uniformly dispersed in water, and
The mobility of water-coal-slurry is improved, dosage is about the 1% of coal.In general, dispersing agent is a kind of surfactant.Common surface
Activating agent has sulfonate type segregant surfactant (such as lignosulfonates tea sulfonate, alkenyl sulfonate), polyoxy second
Alkene punishment is non-from surfactant, water soluble polymer f polymer and anion surface active column and non-ionic surface active
The compound of agent.(2) stabilizer: water-coal-slurry is one kind after all by solid, liquid two-phase coarse dispersion system, and coal grain is easy to spontaneously again
It coalesces each other.Under gravity or other outer plus mass force effects, precipitating occurs and is inevitable.To prevent to precipitate firmly,
A small amount of stabilizer must be added in water-coal-slurry.Stabilizer acts on of both having, and water-coal-slurry is on the one hand made to have shear shinning
Rheological behavior, i.e., have higher viscosity when the static storage of water-coal-slurry, start flowing after viscosity can lower rapidly again；It is another
Aspect makes sediment have soft structure, prevents expendable hard precipitating.
Preferably using the low-order coal of powdery as raw material in the present invention, convenient for improving the efficiency of drying, drying generally can only
Most Free water in low-order coal is removed, and cannot generally remove the combination water in low-order coal, therefore, low-order coal passes through drying
Low-order coal and exhaust gas after being dried after process, the low-order coal after gained drying still contain a certain amount of moisture, this
The moisture of some residual can gasify in subsequent gasification reducing process and become vapor.Have one simultaneously during drying
The low-order coal of part small grain size is entered in exhaust gas in the form of fugitive dust, this part fugitive dust is the first coal dust, raw material low-order coal
Granularity is smaller, and the first coal dust in exhaust gas is more, and exhaust gas direct emission not only polluted environment, wastes coal resource, therefore
The first coal dust in exhaust gas after capturing recycling stoving process by the first dust collecting process has important economic value.It is general logical
Cross in the first dust collecting process exhaust gas recycling 95% or more the first coal dust.
Low-order coal after drying enters gasification reducing process and reacts to obtain the gas mixture of high temperature.Wherein, gasify
Reducing process is the chemical reaction process heated under anaerobic or micro-oxygen conditions to the low-order coal after drying.It is low after drying
Rank coal enters gasification reducing process, under the heating of the heat mediums such as flue gas, in reaction process without be added additive etc. other
Substance, temperature are generally 350 DEG C -800 DEG C, and the process of complex chemical reaction occurs under pressure≤30Kpa, obtain solid carbon and
The gas mixture of high temperature, wherein solid carbon is upgraded coal, the volatile matter 8-15wt% in upgraded coal.The oil gas of high temperature
Mixture is to include CO, H2、CO2, hydro carbons, coal tar, dust and sulfur-containing compound etc. more foreign gases.
The source of oxygen is mainly in the following several ways in the anaerobic or micro- oxygen environment that reducing process uses that gasify: (1), raw material
Gap inside low-order coal, the air of the gap entrainment between material and material；(2) from gasification reducing process feed inlet, go out
Material mouth etc. reveals mixed a small amount of air；(3), coal is accounted for hereinafter, can slightly be passed through in gasification reducing process in explosion limit value
The O of charcoal mass percent 5%2Or (air), further preferably it is passed through the O for accounting for Coal Quality percentage 3%2Or (air),
Be conducive to improve temperature, the slagging prevention etc. of gasification reduction reaction, and ensure that entire gasification reducing process reaction simultaneously
Security and stability；It is preferred that the low-order coal after drying carries out gasification reduction reaction in oxygen-free environment, the low-order coal after avoiding drying
Combustion reaction occurs with oxygen in entering gasification reducing process reaction process, generates a large amount of aphlogistic CO2, to guarantee
CO in the gas mixture of obtained high temperature2Deng volume basis it is smaller, it is mixed to be conducive to the subsequent oil gas for preparing high-energy density
Object is closed, and processing step is few, it is simple to operation, so that reaction can carry out safely.It is remaining in low-order coal after drying
Moisture enters the gas mixture of high temperature as water vapor, contains CO, H in gas mixture2、CO2, hydro carbons, dust, water
Steam, coal tar and sulfur-containing compound etc.；Gas mixture passes through the second dust collecting process again and removes dust, the ash that this part is removed
Dirt can return in gasification reducing process that the reaction was continued, after dedusting remaining gas pass through again the processing of oil gas cooling technique make it is a large amount of
Vapor and coal tar etc. are cooling to obtain the oil water mixture of liquid, and oil water mixture is handled using water-oil separating, i.e.,
Available first waste water；The first waste water, slurries additive agent and the first coal dust are mixed and made into flowable solution again, can be obtained
To water-coal-slurry；Finally again by water-coal-slurry and O2It is obtained together by coal-water slurry gasification comprising CO and H2Water-gas, water-coal-slurry
In gasification process is mainly by the coal substance (i.e. fixed carbon) and O in water-coal-slurry2The either oxygen burnup heat release of high-purity,
Coal substance is reacted with the water in water-coal-slurry generates CO and H2, to prepare water-gas.High organic content in first waste water, ingredient
Complexity causes cost for wastewater treatment high, and the first useless water reuse solves the problems, such as discharged wastewater met the national standard difficulty；In addition, because
For the single utilization of the first coal dust, utilization rate is low, transports easy fugitive dust；Therefore water-gas is prepared using the method in the present invention, given up
Object utilizes, and economizes on resources.Impurity gas is removed due to containing the impurity such as a certain amount of dust in water-gas, then by purification process
Body recycles shift conversion technique to increase the H in water-gas2Percent by volume.
Preferably, by-product when CO described in step (5) and nitrous acid ester pass through carbonylation coupling process synthesis of diethyl oxalate employing
NO and alcohols, the NO and alcohols are as the regenerated raw material of nitrous acid rouge.It is closed with nitrous acid ester by carbonylation coupling process in CO
It is NO and alcohols etc. at by-product while diethy-aceto oxalate, NO and alcohols pass through the raw regeneration nitrous acid of oxidative esterification reaction
Rouge, by-product recycle, reduce the dosage of intermediate raw material nitrous acid rouge, be conducive to green and healthy Chemical Manufacture.
Preferably, shift conversion technique described in step (4) be by CO in the water-gas by with H2O response transform turns
Turn to H2And CO2Technique.Shift conversion reaction are as follows: CO+H2O H2+CO2If CO too high levels in water-gas, hydrogen is less,
By vapor (H2O it) is passed through in water-gas and makes CO and H2Shift conversion reaction occurs for O, and operation in this way can increase active principle
H2Amount.
Preferably, the reaction temperature of gasification reducing process described in step (2) is 350-800 DEG C.At this temperature, it dries
The volatile matter in low-order coal after dry is escaped from low-order coal, so that the gas mixture of high temperature is obtained, after the reduction reaction that gasifies
Remaining solid residue is the upgraded coal with temperature, and the volatile matter content in upgraded coal is 8-15wt%.Wherein, gasification reduction work
Skill can be level-one, or multistage.When using level-one gasification reducing process, primarily to obtaining most of high temperature
Gas mixture, the height of temperature directly affect the temperature of subsequent gas production, the yield of upgraded coal and level-one upgraded coal；Work as use
When multistage gasification reducing process, multistage gasification reducing process main function is can not gasify in upper level gasification reducing process
Solid matter (including gasification after fine coal, solid impurity etc.), it is a certain amount of, can not gasifying within certain residence time,
The higher boilings grease such as similar pitch continue gasification and the residence time it is short have little time to be precipitated or temperature be not achieved phenolic compound,
The polycondensation reaction condition of arene compound etc., gasification that the reaction was continued are conducive to the quality for improving gas yield and upgraded coal.
Preferably, the granularity of the first coal dust described in step (1) is less than 1mm.Water-coal-slurry preparation first have to by coal substance into
Row fine grinding, the first coal dust in exhaust gas generated during stoving process due to raw material of the present invention, is removed through first
95% or more the first coal dust in dirt technique exhaust gas recycling, the first coal powder size are generally less than 3mm, and preferred size is less than 1mm
The first coal dust as it is subsequent production water-coal-slurry raw material, the first coal dust is mixed with the first waste water, additive, at grinding
Water-coal-slurry can be obtained in reason, saves processing step, and greatly reduce the cost of coal pulverizer, improves the use of coal pulverizer
Service life.Still further preferably, the first coal dust of fine coal partial size≤50 μm.
Preferably, remaining gas passes through condensation work after exhaust gas described in step (1) being handled by the first dust collecting process
Skill handles to obtain the second waste water, water-coal-slurry described in step (4) include second waste water, the first waste water described in step (3),
First coal dust and slurries additive agent described in step (1).Boil-off gas in the first coal dust and drying course is mainly contained in exhaust gas
The vapor of change, the source of water when this part vapor condensing recovery gets up can also be used as preparation water-coal-slurry, to supplement the
The shortage of water resource when one waste water is inadequate, while also improving the utilization rate of water resource in low-order coal.
Preferably, the low-order coal after drying described in step (2) also obtains upgraded coal by gasification reducing process processing, institute
State that upgraded coal is screened to obtain the second coal dust, the granularity of second coal dust is less than 1mm；Water-coal-slurry described in step (4) includes
First waste water described in second coal dust, step (3), the first coal dust and slurries additive agent described in step (1).
Preferably, gas mixture described in step (3) passes sequentially through the second dust collecting process and the processing of oil gas cooling technique
Greasy filth is also obtained, water-coal-slurry described in step (4) includes institute in the first waste water described in the greasy filth, step (3), step (1)
State the first coal dust and slurries additive agent.The upgraded coal granule size that reducing process generates in the process that gasifies is different, especially grain
Spend lesser upgraded coal, it has not been convenient to transport, be easy to cause environmental pollution, therefore upgraded coal is sieved and obtains granularity less than 1mm's
Second coal dust, the supplement of the coal resource as preparation water-coal-slurry, the upgraded coal of granularity less times greater than 1mm directly can sell or store up
The standby energy.
Preferably, water-coal-slurry and O described in step (4)2Before being handled by coal-water slurry gasification, the water-coal-slurry is first
By filter pulp process again with O2It is obtained by coal-water slurry gasification comprising CO, CO2And H2Water-gas.Considering slurry purpose is
The coarse granule occurred during water-coal-slurry processed and the certain sundries for being mixed into slurry are removed, to prevent water coal slurry in storage and transportation and burning
Blocking pipeline and nozzle etc. in the process.
Preferably, process for separating and purifying described in step (5) includes Deep Cooling Method and pressure-variable adsorption.Due to the present invention to CO and
H2 purity it is more demanding, the purity of H2 is difficult to separate completely not less than both 99.9%, CO and H2, generally first uses Deep Cooling Method
Separating-purifying CO recycles Pressure Swing Adsorption H2, to meet for producing ethylene glycol to the quality requirement of H2.The side of H2 purification
Method mainly has pressure swing adsorption hydrogen production and UF membrane hydrogen manufacturing etc..Membrane separating method is not able to satisfy the purity requirement of product hydrogen, therefore
It is preferred that the method for pressure swing adsorption hydrogen production.
Based on above technical scheme, the method in the present invention effectively recycles waste water in low-order coal, entire technical process
Coal dust and greasy filth of middle generation etc. recycle water-coal-slurry to prepare ethylene glycol, waste recycling not only solves for making water-coal-slurry
The problem for discharged wastewater met the national standard difficulty of having determined；And it solves coal dust and utilizes difficult circumstances pollution problem；In addition, being utilized simultaneously
The substances such as the byproduct greasy filth in technical process realize a variety of refuse reclamations, meet the coal high-efficiency that country advocates energetically
Clean utilization；
In addition, being that raw material prepares ethylene glycol with waste water etc., low in cost, reaction condition is mild, before having huge market
Scape can both meet market demands, can also improve China's ethylene glycol supply and marketing pattern, reduce the degree that ethylene glycol relies on import.
Detailed description of the invention
It, below will be in embodiment in order to illustrate more clearly of embodiment in the present invention or technical solution in the prior art
Required attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only one recorded in the present invention
A little embodiments are also possible to obtain other drawings based on these drawings for those of ordinary skill in the art.
Fig. 1 is a kind of with waste water water-coal-slurry and by the signal of the process of the method for water-coal-slurry preparing ethylene glycol in the present invention
Figure.
Specific embodiment
Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art.
Method in following embodiments is unless otherwise instructed the conventional method of this field.In addition, term " first ", " second " etc.
It is only used for distinguishing description, is not understood to indicate or imply relative importance.
As shown in Figure 1, the invention discloses a kind of with waste water water-coal-slurry and passes through the method for water-coal-slurry preparing ethylene glycol, it should
Method the following steps are included:
(1) low-order coal handles the low-order coal after being dried and exhaust gas by stoving process, and the exhaust gas is through the first dedusting
Technique obtains the first coal dust；
(2) low-order coal after drying described in step (1) is handled to obtain gas mixture by the reducing process that gasifies, institute
Stating gasification reducing process is the chemical reaction process heated under anaerobic or micro-oxygen conditions to the low-order coal after drying；
(3) gas mixture described in step (2) is passed sequentially through into the second dust collecting process and oil gas cooling technique is handled, obtained
To the first waste water；
(4) water-coal-slurry includes the first waste water described in step (3), the first coal dust and water-coal-slurry described in step (1)
Additive, by the water-coal-slurry and O2It handles to obtain comprising CO, CO by coal-water slurry gasification2And H2Water-gas, the water
Coal gas passes sequentially through purification process and shift conversion process obtains synthesis gas；
(5) CO and H are respectively obtained after handling synthesis gas described in step (4) by process for separating and purifying2；The CO with
Nitrous acid ester by carbonylation coupling process synthesis of diethyl oxalate employing, the diethy-aceto oxalate again with the H2Hydrogenation reaction is carried out to obtain
To thick ethylene glycol, the thick ethylene glycol obtains the ethylene glycol after passing through Purification Catalysts of Monoethylene Glycol.
Water-coal-slurry is a kind of environmental clean fuel of New type coal base flow body, burning of coal characteristic has both been remained, but also with class
It is the real clean coal technology in one, current China like the liquid-phase combustion application characteristic of heavy oil.Water-coal-slurry by 65-70% coal,
The water of 29-34% and chemical addition agent less than 1%, are made by certain processing technology, appearance picture oil, good fluidity,
It stores general 3-6 months and does not precipitate, convenient transportation, high combustion efficiency, pollutant (SO2、NOX) discharge is low, about 2t water-coal-slurry can be with
1t fuel oil is substituted, can be used in the generation oil such as Industrial Boiler, station boiler and Industrial Stoves or coal, gas；Water-coal-slurry crosses water-coal-slurry gas
Chemical industry skill prepares CO and H2, it is the indispensable conversion gas for preparing ethylene glycol etc..
1 water-coal-slurry of table, heavy oil, natural gas unit calorific value, price comparison sheet
| Title | Calorific value (MJ/Kg) | Price (member/t) | Unit calorific value price (member) |
| Water-coal-slurry | 18-20 | 350 | 0.019-0.017 |
| Heavy oil | 40.98 | 1500-1800 | 0.037-0.044 |
| Natural gas | 36.12(MJ/Nm3) | 1.7 (members/Nm3) | 0.054 |
As shown in Table 1, the unit calorific value price of water-coal-slurry is lower, therefore it is next to can be used as a kind of very economical calorific value
Source.
From the point of view of the long term growth of water-coal-slurry industry, pulping raw material should be based on cheap jet coal, weakly caking coal, no
The high-orders coals such as low-order coals and anthracite, meager coal, poor Of-thin coal such as glutinous coal, lignite, or such as municipal sludge, industrial sludge, coal slurry flotation
Etc. various solid waste, the economy of water-coal-slurry not only can be improved, also comply with and national rationally utilize coal and waste resource
Policy.
Slurries additive agent mainly includes viscosity reduction dispersing agent and stabilizer.Wherein dispersing agent is mostly important, it is directly affected
The quality and preparation cost of water-coal-slurry.(1) dispersing agent: the surface of coal has strong hydrophobicity, cannot be intimately associated with water
As a kind of slurry, a kind of wet walk only will form in higher concentration.A small amount of dispersing agent is added in slurrying and changes coal
The surface nature of grain, making coal particle surface tightly is that additive molecule and hydration shell surround, and coal grain is allowed to be uniformly dispersed in water, and
The mobility of water-coal-slurry is improved, dosage is about the 1% of coal.In general, dispersing agent is a kind of surfactant.Common surface
Activating agent has sulfonate type segregant surfactant (such as lignosulfonates tea sulfonate, alkenyl sulfonate), polyoxy second
Alkene punishment is non-from surfactant, water soluble polymer f polymer and anion surface active column and non-ionic surface active
The compound of agent.(2) stabilizer: water-coal-slurry is one kind after all by solid, liquid two-phase coarse dispersion system, and coal grain is easy to spontaneously again
It coalesces each other.Under gravity or other outer plus mass force effects, precipitating occurs and is inevitable.To prevent to precipitate firmly,
A small amount of stabilizer must be added.Stabilizer acts on of both having, and the rheology on the one hand making water-coal-slurry have shear shinning is special
Property, i.e., there is higher viscosity when the static storage of water-coal-slurry, viscosity can lower rapidly again after starting flowing；On the other hand make to sink
Starch has soft structure, prevents expendable hard precipitating.
Raw material low-order coal of the invention can be fine coal and be also possible to lump coal, when low-order coal uses lump coal, to bulk excessively
Coal can be by broken, screening process to obtain the lesser fine coal of granularity.It is preferred that using fine coal as raw material, be on the one hand because of
Fine coal is no longer needed to through broken, screening process, saves processing step, and heating surface area is big when drying, and drying efficiency is high, is on the other hand
Fine coal is cheap with respect to lump coal, it is preferred to use granularity is less than the fine coal of 20mm, still further preferably using granularity less than 6mm's
Fine coal.
Drying can only generally remove most Free water in low-order coal, and cannot remove the combination water in low-order coal, because
This, low-order coal by stoving process handle after dry after low-order coal and exhaust gas, gained dry after low-order coal still contain
There is a certain amount of moisture, the moisture of this some residual can gasify in subsequent gasification reducing process becomes vapor.If low order
Contain a large amount of moisture in coal, heat consumption is big during will lead to gasification reduction reaction, and therefore, technical solution of the present invention is preferred
The portion of water first removed in low-order coal is handled by stoving process to low-order coal.The drying medium of stoving process can be
Flue gas or vapor, drying can be divided into directly drying and indirect drying.When using flue gas as medium is dried, although flue gas
The efficiency of the drying directly contacted with low-order coal is highest, but while being dried using flue gas wants strict control stoving process
For the percent by volume of oxygen in explosion limit hereinafter, to prevent detonation, the efficiency of flue gas indirect drying is also unsatisfactory in environment,
Therefore for production safety and drying efficiency, preferably vapor is dried.Vapor directly dries and is easy to be likely to result in vapor
It is mixed into and in low-order coal, not only causes the consumption of reaction coal resource, and reduce drying efficiency, therefore indirect using vapor
The drying mode of low-order coal is dried, to prevent the moisture in water steam from entering in low-order coal.In addition, if water steams in drying course
Atmospheric pressure is excessive, and vapor bring temperature is excessively high to be easy to cause during the drying process, and part volatile matter can escape in low-order coal
Out, the evolution of one side volatile matter can bring security risk, on the other hand will affect the gas production of subsequent gasification reducing process,
Therefore drying steam pressure is not easy excessive in drying course, to guarantee not only to can guarantee drying effect, but also can guarantee in low-order coal
Volatile matter do not gasified.It is preferred, therefore, that stoving process uses water vapour indirect drying, the pressure of water vapour is 0.3-
1.5Mpa, the temperature of water vapour are 105-250 DEG C, can maximumlly be reduced under this process condition aqueous in low-order coal
Rate, it might even be possible to so that being reduced to 7wt% from the water content in the low-order coal that the discharge port of stoving process is discharged hereinafter, big at this time
Partial moisture is escaped from low-order coal along with fugitive dusts such as the powdery low-order coals of small grain size, and is entered as water vapor
In the exhaust gas generated after drying, the outlet mass temperatures of stoving process are 50-150 DEG C；Still further preferably, when the pressure of vapor
Power is 0.6-1.2Mpa, when the temperature of vapor is 120-200 DEG C, after drying the moisture content of low-order coal will decrease to 6wt% with
Under, the outlet mass temperatures of stoving process are 80 DEG C -130 DEG C.
Stoving process of the invention can be level-one, or it is multistage, because if low-order coal after level-one stoving process
Moisture content still reach to the requirement less than technique, can be continued using multistage dry such as second level drying, three-level stoving process into one
Drying is walked, until the moisture content of low-order coal meets process conditions after drying.In addition, multistage stoving process can be arranged in series
It can also be arranged in parallel, drying effect can be reinforced when connecting using multistage stoving process, stoving process can be increased when in parallel
Treating capacity therefore according to the demand of actual production technique be series connection to multistage stoving process or in parallel in parallel or in series
Design simultaneously, can be adjusted according to the actual situation, as long as identical technical effect can be reached, specifically, for example,
When the inlet amount of stoving process is in terms of the low-order coal of 20-30t/h, level-one steam drying technique can be used；When stoving process into
Second steam stoving process can be used in terms of the low order of 50-70t/h in doses, more economical reasonable in this way.
Exhaust gas in drying course mainly includes the low-order coal of small grain size and the vapor that drying is removed, raw material low-order coal
Granularity is smaller, and the coal dust in exhaust gas is more, and exhaust gas direct emission not only polluted environment, wastes coal resource, therefore pass through
The coal dust in exhaust gas after first dust collecting process recycling stoving process has important economic value.It can be returned through the first dust collecting process
In exhaust gas 95% or more coal dust, referred to herein as the first coal dust are received, the first coal powder size is generally less than 3mm, and preferred size is less than
The first coal dust of 1mm is mentioned as the raw material of subsequent production water-coal-slurry with reducing the grinding technics to large particulate matter in water-coal-slurry
The high service life and efficiency of grinder.Preferably, exhaust gas through the first dust collecting process processing after remaining gas again through condensing
Process obtains the second waste water, and the second waste water of this part can also be used as the raw material of the water resource of subsequent preparation water-coal-slurry,
To make full use of all moisture in low-order coal.
Low-order coal after being dried by stoving process enters gasification reducing process and is reacted, in order to advanced optimize work
Skill, low-order coal after the drying can also add gasification feeding process before entering gasification reducing process, so as to low after drying
Rank coal rapidly enters gasification reducing process, increases the surface area of material, is conducive to accelerate gasification reduction reaction.
Wherein, gasification reducing process is that the chemistry that is heated under anaerobic or micro-oxygen conditions to the low-order coal after drying is anti-
Answer technique.Low-order coal after drying is delivered to gasification reducing process, under the heating of the heat mediums such as flue gas, nothing in reaction process
Other substances such as additive need to be added, temperature is generally 350 DEG C -800 DEG C, complex chemical reaction occurs under pressure≤30Kpa
Process obtains the gas mixture of solid carbon and high temperature, and solid carbon is the upgraded coal for having certain temperature, upgraded coal
Temperature is 350 DEG C -800 DEG C.The gas mixture of high temperature is to include CO, H2、CO2, hydro carbons, coal tar, dust and sulfur-containing compound
Deng more foreign gases.
Wherein, the source of oxygen is mainly in the following several ways in the anaerobic or micro- oxygen environment that gasification reducing process uses:
(1), the gap inside raw material low-order coal, the air of the gap entrainment between material and material, the O in the air of this part2?
It is reacted immediately with coal in the environment of gasification reducing process high temperature and generates CO2Or CO；(2) from gasification reducing process feed inlet,
Discharge port etc. reveals mixed a small amount of air, the oxygen of this partial air, the micro O in this part2It is high in gasification reducing process
It is reacted immediately with coal under the environment of temperature and generates CO2Or CO；(3), in explosion limit value hereinafter, can be slightly in gasification reducing process
It is passed through the O for accounting for Coal Quality percentage 5%2Or (air), 1. this operation, which has the advantage that, can be improved gasification reduction work
Temperature and capacity usage ratio in skill；2. improving the conversion ratio of charcoal；3. preventing coal coking；4. a small amount of O2It is incomplete with low-order coal
Burning produces more CO.Since gasification reducing process internal temperature is higher, a small amount of O being passed through2It is anti-that oxidation can occur for moment
It answers (including combustion reaction), the burning point of many combustibles is all below the reaction temperature of gasification reduction reaction.Because CO and air are mixed
It closes explosion and is limited to 12%-74.2%；H2Explosion value is 4%-75%.O2Accounting for AIR Proportional is 21%.O after conversion2Explosion limit
Upper value is 6% or so.By theoretical calculation, the coal of 100kg can generate about 80Nm3CO and H2.Coal Quality is accounted for so being passed through
The O of percentage 5%2It is safe；Still further preferably, it is passed through the O for accounting for Coal Quality percentage 3%2, to ensure entirely to gasify
The security and stability of reducing process reaction.But it when the temperature for the reduction reaction that gasifies meets technique requirement, can not also be passed through
Oxygen, the low-order coal after preferably drying carry out gasification reduction reaction in oxygen-free environment, so that reaction can carry out safely.
Wherein, gasification reducing process can be level-one, or multistage.It is main when using level-one gasification reducing process
If in order to make remaining moisture after volatile matter and the drying in low-order coal sufficiently gasify most of high temperature gas mixture,
The height of temperature directly affects subsequent gas production etc., and the reaction temperature for the reducing process that gasifies is 350 DEG C -800 DEG C, when using multistage
Gasify reducing process when, multistage gasification reducing process main function be upper level gasification reducing process in can not gasify consolidate
Body substance (including fine coal, the solid impurity etc. after gasification), a certain amount of pitch etc. that can not gasify within certain residence time
Higher boiling grease and residence time short have little time to be precipitated or the contracting of phenolic compound, arene compound etc. is not achieved in temperature
Poly- reaction condition, gasification that the reaction was continued are conducive to the quality for improving gas yield and upgraded coal.
Other than the temperature of guarantee gasification reducing process is reasonable, while it must also guarantee certain in gasification reducing process stop
The time is stayed, the residence time is too short, and the also not evolution gasification completely such as volatile matter and moisture influences the yield of gas；Residence time is too
Long, although product is guaranteed, yield is not caught up with, so being kept for a reasonable gasification reduction reaction residence time to production
Product yield is most important.Since the kind of raw material low-order coal is different, the residence time of material is in the general reducing process that gasifies
30min-4h。
Preferably using two-stage gasification reducing process in the present invention, the material after stoving process drying is introduced into level-one gasification also
Original process enter back into second level gasification reducing process, and the low-order coal after drying is introduced into level-one gasification reducing process and obtains level-one gas
With level-one solid, level-one solid enter back into second level gasification reducing process continue gasification obtain secondary gas and second level solid, second level
Solid is upgraded coal；The feeding temperature of level-one gasification reducing process is 80 DEG C -120 DEG C, and air outlet temperature is 180 DEG C -550 DEG C,
Reaction temperature is 450 DEG C -650 DEG C, and drop temperature is 350 DEG C -600 DEG C；The feeding temperature of second level gasification reducing process is
350 DEG C -600 DEG C, drop temperature is 450 DEG C -750 DEG C, and reaction temperature is 550 DEG C -800 DEG C, and air outlet temperature is 450 DEG C -700
℃.When using two-stage gasification reducing process, primarily to most of volatile is made to be gasified totally, it can obtain a large amount of
Gas can obtain the lower upgraded coal of volatile matter again, and wherein the volatile matter content in upgraded coal is 3-8wt%.
In addition, different due to obtaining upgraded coal granule size from gasification reducing process, the especially lesser upgraded coal of granularity,
Moisture-free, it has not been convenient to transport, be easy to cause environmental pollution, therefore upgraded coal is sieved to the second coal for obtaining granularity and being less than 1mm
Powder, the supplement of the coal resource as preparation water-coal-slurry, the upgraded coal of granularity less times greater than 1mm directly can sell or do deposit energy
Source.
Because the low-order coal after drying obtains the coal dust in high-temperature oil gas after the reduction reaction that gasifies, most of to be all
Fine dust is either practically free of the solid particle etc. of volatile matter, contains more high-ash solid coal dust.This part coal dust
Into a large amount of greasy filth is generated in oil water mixture, because of oil-in-water, the interaction of Water-In-Oil, coal dust should compare table containing a large amount of
Area plays good Action of Surfactant, so that oil water mixture becomes abnormal sticky, leads to oil, water, coal dust very
Hardly possible separation, it is therefore desirable to which the second dust collecting process is to remove a large amount of coal dust in high-temperature oil gas.The coal that second dust collecting process is removed
Dirt, largely may return to gasification reducing process, the reaction was continued, and the dust generated when maintenance when appliance arrangement chamber clean is available
Make the raw material of preparation water-coal-slurry.
Preferably gasified reducing process using two-stage in the present invention, every grade of gasification reducing process is distinguished successively with respective second
Dust collecting process is connected with oil gas cooling technique；The amount of dust in high-temperature oil gas generated after every grade of gasification reduction is larger, therefore, is
Technique is advanced optimized, every grade of gasification reducing process is first connect with respective second dust collecting process, every grade of the second dedusting work
Skill is connect with same set of oil gas cooling technique again, to save process procedure.
Since stoving process cannot completely remove the moisture in low-order coal, the freedom being generally in low-order coal that can be removed
Water, alternatively referred to as free water, including free moisture and inherent moisture, in the majority with free moisture, the combination water in low-order coal can not
It is removed by drying, therefore obtained in the gas mixture of high temperature from gasification reducing process containing a certain amount of vapor, water
The measurer body of steam is related with the type of low-order coal and drying degree, is generally not more than the 15wt% of raw material low-order coal；High temperature
Gas mixture, which first passes through, to be entered back into oil gas cooling technique after the second dust collecting process dedusting and obtains the first waste water, due to the oil of high temperature
While cooling, gaseous coal tar also is cooled vapor simultaneously in gas mixture, and being handled by water-oil separating will
Oil separates to obtain the first waste water, coal tar and a small amount of greasy filth with water.In the first waste water, still contain a small amount of coal tar
Oil, mainly exists in the form of oil-in-water, and COD (COD) is even higher between 5000mg/L~100000mg/L；
First waste component is complicated, contains phenols, oil and ammonia nitrogen etc..Wherein, phenols mainly contains methyl class phenol, catechol, benzene two
The aromatic hydrocarbon substance of the complexity such as phenol.The salinity of first waste water is very high, and various ion concentrations are high, especially the content of high price example
More prominent, this will bring significant impact to the performance of water-coal-slurry.Phenols has certain acidity mostly, with the of high salinity
One waste water slurrying, it is difficult to which the requirement for reaching high-concentration coal-water slurry can mitigate high mineralization due to the presence of the first Phenol for Waste Water class
The destruction to coal slurry mobility is spent, therefore, the first waste water energy containing phenols improves water-coal-slurry performance.
It is on the one hand that the middle impurity in the first waste water is more using the first waste water as the source of production water-coal-slurry water, place
Reason discharge is difficult, is used as preparation water-coal-slurry, not only solves the problems, such as sewage discharge difficulty, and be effectively utilized water resource,
The especially original shortage of water resources in the Northwest；It compared with pure industrial water, is contained in the first waste water on the other hand
The substances such as a small amount of coal tar, phenols, lime-ash, the presence of the substances such as phenols are conducive to water-coal-slurry and are slurried, coal tar and lime-ash
The presence of equal substances increases the energy value of water-coal-slurry.
In the present invention, the main source for preparing the water of water-coal-slurry is the first waste water, and the source of coal substance is mainly first
Coal dust.
By above-mentioned first waste water, the first coal dust is mixed with slurries additive agent solution, and water-coal-slurry can be obtained, water-coal-slurry
Concentration is greater than 64.1wt%；Viscosity is less than 1200mPas (at 20 DEG C of slurry temperature, shearing rate 100S-1)；Calorific value is greater than
18.51MJ/kg。
In addition, the present invention, which can also be used in technical process, generates other coal substances and water resource as preparation water-coal-slurry
Raw material.
Preferably, the exhaust gas that will be generated in drying course, remaining gas passes through again after first passing through the processing of the first dust collecting process
Condensation process handles to obtain the second waste water, the source of water when the second waste water can also be used as preparation water-coal-slurry, to supplement first
The shortage of water resource when waste water is inadequate, while also improving the utilization rate of water resource in low-order coal.Second waste water, first are given up
Water, the first coal dust are mixed with slurries additive agent, obtain water-coal-slurry.
Preferably, the upgraded coal reducing process that gasifies handled, the upgraded coal that gasification reducing process generates in the process
Granule size is different, especially the lesser upgraded coal of granularity, it has not been convenient to transport, be easy to cause environmental pollution, therefore by upgraded coal
Screening obtains the second coal dust that granularity is less than 1mm, and the supplement of the coal resource as preparation water-coal-slurry, granularity is less times greater than 1mm's
Upgraded coal directly can sell or do stored energy source.Supplemental resources of this second coal dust of part as coal substance in preparation water-coal-slurry.
Second coal dust, the first waste water, the first coal dust are mixed with slurries additive agent, obtain water-coal-slurry.
Preferably, using the greasy filth generated in oil gas cooling procedure as the source of the coal substance of preparation water-coal-slurry.Greasy filth master
If substances such as tiny coal dust, coal tar and waste water, oil-sludge treatment discharge is difficult, and be easy to cause the wave of resource in greasy filth
Take, greasy filth is used as preparation water-coal-slurry, can make full use of the resource in greasy filth.By greasy filth, the first waste water, the first coal dust and water coal
Additive mixing is starched, water-coal-slurry is obtained.
As the further improvement of technique in the present invention, in water-coal-slurry and O2Before being handled by coal-water slurry gasification, water
Coal slurry first through filter pulp again with O2It is obtained by coal-water slurry gasification comprising CO and H2Synthesis gas.Considering slurry purpose is to remove making
The coarse granule occurred during water-coal-slurry and the certain sundries for being mixed into slurry, to prevent water coal slurry from blocking up in storage and transportation and combustion process
Fill in pipeline and nozzle etc..
Finally, again by the water-coal-slurry and O of above-mentioned preparation2It is obtained together by coal-water slurry gasification comprising CO and H2Water
Coal gas, the coal substance and O in key reaction water-coal-slurry in coal-water slurry gasification2In burnup heat release, coal substance and water-coal-slurry
Water reaction generate CO and H2.Here O2It can be pure oxygen, be also possible to the oxygen rich gas of high-purity.Coal substance and H2O (water
Steam) reaction be the endothermic reaction, reaction equation C+H2O=CO+H2, first it is passed through O2So that a part of a small amount of water-coal-slurry
In coal substance combustion heat release so that environment temperature is rapidly achieved 800-1300 DEG C, then be passed through another part water-coal-slurry and water
Steam reacts at this temperature generates CO and H2, obtained gas is water-gas.In the actual production process, general using continuous
Uninterruptedly it is passed through O2And vapor, so that coal substance and H in water-coal-slurry2O (vapor) reaction is continual to prepare water coal
Gas.Due to containing the impurity such as a certain amount of dust in water-gas, water-gas passes through the water after being purified after purification process processing
Coal gas gas.Purification process mainly includes cyclone dust removal, water scrubber and waste heat boiler etc..
Purified water-gas enters shift conversion technique and is handled to obtain synthesis gas.Water-gas is the water coal by liquid
Obtained by slurry gasification, containing a large amount of remaining vapor after the gasification in water-coal-slurry, it is anti-that this part vapor can be used as shift conversion
Convenient for CO and vapor shift conversion reaction, key reaction are as follows: CO+H occur for the raw material answered2O CO2+H2.The thermal effect of this reaction
H should be regarded2Then it is the endothermic reaction if liquid water depending on the state of O, is then exothermic reaction if vapor.Due to synthesizing second
The raw material of glycol needs H2Molar equivalent ratio with CO is 2:1, H after coal water slurry gasification2It is more general than theoretical value with the molar equivalent of CO
Less than 1:1, and shift conversion reaction is reversible reaction, and the equilibrium constant reduces with the increase of pressure, can be increased in gas
H2Percentage by volume, reduce the percentage by volume of CO, it is possible to increase H2With the molar equivalent ratio of CO, be conducive to subsequent preparation second two
Alcohol.
The country prepares ethylene glycol by raw material of coal at present, mainly there is three process routes:
(1) direct method: with coal gasification producing synthesis gas (CO+H2), then by the direct synthesizing glycol of one step of synthesis gas.This skill
The key of art is the selection of catalyst, is difficult to realize industrialize within quite long period.
(2) olefin processes: using coal as raw material, by obtaining synthesis gas after gasification, transformation, purification, through methanol-fueled CLC, methanol system
Alkene (MTO) obtains ethylene, then finally obtains ethylene glycol through ethylene epoxidizing, ethylene oxide hydration and product exquisiteness.The process
Coal-to-olefin is combined with conventional petroleum route ethylene glycol, technology is more mature, but the cost is relatively high.
(3) oxalic acid ester process: using coal as raw material, by respectively obtaining CO and H after gasification, transformation, purification and separating-purifying2,
Wherein CO is coupled synthesis and purification production oxalate by carbonylation, then passes through and H2Carry out hydrogenation reaction and by being gathered after purification
The process of ester grade ethylene glycol.
Ethylene glycol is prepared using oxalate method in the present invention, takes second two through hydrogenation of oxalate for preparing by low-order coal producing synthesis gas from coal
Alcohol (by taking methanol as an example) mainly comprises the steps that
(1) esterification unit: NO and O2Production methyl nitrite is reacted with alcohols.
2CH3OH+2NO+1/2O2=2CH3ONO+H2O；
The reaction for preparing methyl nitrite is easy to carry out, and does not need catalyst, reaction temperature is between 30~90 DEG C, instead
Answering pressure is 1~5atm.
(2) carbonylation coupling member: CO and methyl nitrite occur carbonylation oxidative coupling reaction and generate dimethyl oxalate.
2CO+2CH3ONO=(COOCH3)2+2NO；
The reaction carries out under Pd/Al2O3 catalyst action, and reaction temperature is between 120~150 DEG C, reaction pressure 1
~5atm.
(3) hydrogenation unit: Hydrogenation of Dimethyl Oxalate generates ethylene glycol.
(COOCH3)2+4H2=(CH2OH)2+2CH3OH；
Total chemical equation: 2CO+4H2+1/2O2=(CH2OH)2+H2O。
Hydrogenation reaction is in Cu/SiO2It is carried out under the action of equal catalyst, reaction temperature is 190~220 DEG C, and reaction pressure is
20~30atm, reaction condition mitigate, and the conversion ratio and selectivity of ethylene glycol are all higher.High activity, highly selective, high stability
Cu/SiO2 catalyst raw powder can accelerate hydrogenation reaction reaction rate and influence reaction product selectivity.First generation sheet
Hydrogenation catalyst has the characteristics that high-intensitive, high stability；Second generation bar shaped hydrogenation catalyst (industrial application catalyst), is urged
Agent oxalic acid ester conversion rate 100%, glycol selectivity are greater than 95%.Third generation monolithic devices hydrogenation catalyst is further eliminated outer
It extends influence, catalyst activity and stability are substantially better than second generation bar shaped hydrogenation catalyst, therefore preferably adopt in the present invention
With monolithic devices hydrogenation catalyst.
Entire reaction process is practical it can be seen from oxalate hydrogenation formula does not consume alcohols and nitrous acid ester, only
It is by CO, O2And H2Carry out synthesizing glycol, wherein CO and H2Separation, purification from synthesis gas, O2It can be air space division institute
, it can also be the pure oxygen directly bought from the external world, to meet the needs of technique respectively.
(4) refined unit: the not a height of thick ethylene glycol of purity of the ethylene glycol of above-mentioned steps preparation, thick ethylene glycol, which is re-refined, to be obtained
Obtain polyester grade ethylene glycol.
CO and H are respectively obtained after above-mentioned synthesis gas is handled by process for separating and purifying2；CO and nitrous acid ester are passed through into carbonyl
Change coupling process synthesis of diethyl oxalate employing, then by the H of diethy-aceto oxalate and separating-purifying2It carries out hydrogenation reaction and obtains thick second two
Alcohol, the above reaction condition is mild, and the selectivity of ethylene glycol is high.The thick ethylene glycol of gained passes through Purification Catalysts of Monoethylene Glycol again and removes by-product
Object methanol, methyl glycollate, 1,2- butanediol etc. impurity prepare polyester grade ethylene glycol, and the purity of prepared ethylene glycol is
99%, it can be used as a kind of important Organic Chemicals.Wherein, pass through carbonylation coupling process synthesis of oxalic acid in CO and nitrous acid ester
By-product is NO and alcohols etc. while diethylester, and NO and alcohols pass through the raw regeneration nitrous acid rouge of oxidative esterification reaction, by-product
Object recycles, and reduces the dosage of intermediate raw material nitrous acid rouge, is conducive to green and healthy Chemical Manufacture.
In conclusion the present invention recycles the chemical products of coal water slurry gasification system high value processed using waste water preparation water-coal-slurry
Ethylene glycol not only realizes the recycling of waste water, solves the problems, such as that wastewater treatment discharge is difficult, and recycled and be utilized
Coal dust reduces pollution of the coal dust to environment, improves the utilization rate of low-order coal；The byproduct in technical process is utilized simultaneously
The substances such as greasy filth realize a variety of refuse reclamations, meet the coal high-efficiency clean utilization that country advocates energetically；In addition, with useless
Water etc. is that raw material prepares ethylene glycol, and low in cost, reaction condition is mild, has huge market prospects, can both meet market and want
It asks, China's ethylene glycol supply and marketing pattern can also be improved, reduce the degree that ethylene glycol relies on import.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
- With waste water water-coal-slurry and pass through the method for water-coal-slurry preparing ethylene glycol 1. a kind of, it is characterised in that: this method includes following Step:(1) low-order coal handles the low-order coal after being dried and exhaust gas by stoving process, and the exhaust gas is through the first dust collecting process Obtain the first coal dust；(2) low-order coal after drying described in step (1) is handled to obtain gas mixture, the gas by the reducing process that gasifies Changing reducing process is the chemical reaction process heated under anaerobic or micro-oxygen conditions to the low-order coal after drying；(3) gas mixture described in step (2) is passed sequentially through the second dust collecting process and oil gas cooling technique to handle, obtains the One waste water；(4) water-coal-slurry includes the first waste water described in step (3), the first coal dust described in step (1) and water-coal-slurry addition Agent, by the water-coal-slurry and O2It handles to obtain comprising CO, CO by coal-water slurry gasification2And H2Water-gas, the water-gas It passes sequentially through purification process and shift conversion process obtains synthesis gas；(5) CO and H are respectively obtained after handling synthesis gas described in step (4) by process for separating and purifying2；The CO and nitrous Acid esters by carbonylation coupling process synthesis of diethyl oxalate employing, the diethy-aceto oxalate again with the H2Hydrogenation reaction is carried out to obtain slightly Ethylene glycol, the thick ethylene glycol obtain the ethylene glycol after passing through Purification Catalysts of Monoethylene Glycol.
- 2. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: by-product NO and alcohols when CO described in step (5) and nitrous acid ester pass through carbonylation coupling process synthesis of diethyl oxalate employing, it is described NO and alcohols are as the regenerated raw material of nitrous acid rouge.
- 3. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: shift conversion technique described in step (4) be by CO in the water-gas by with H2O response transform is converted into H2And CO2's Technique.
- 4. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: the reaction temperature for the reducing process that gasifies described in step (2) is 350-800 DEG C.
- 5. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: the granularity of the first coal dust described in step (1) is less than 1mm.
- 6. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: remaining gas handles to obtain the by condensation process after exhaust gas described in step (1) is handled by the first dust collecting process Two waste water, water-coal-slurry described in step (4) include institute in the first waste water described in second waste water, step (3), step (1) State the first coal dust and slurries additive agent.
- 7. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: the low-order coal after drying described in step (2) also obtains upgraded coal by gasification reducing process processing, and the upgraded coal is through sieving Get the second coal dust, the granularity of second coal dust is less than 1mm；Water-coal-slurry described in step (4) include second coal dust, First waste water described in step (3), the first coal dust and slurries additive agent described in step (1).
- 8. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: gas mixture described in step (3) passes sequentially through the second dust collecting process and the processing of oil gas cooling technique also obtains greasy filth, walks Suddenly water-coal-slurry described in (4) includes the first coal dust and water described in the first waste water described in the greasy filth, step (3), step (1) Slurry additive.
- 9. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: water-coal-slurry and O described in step (4)2Before being handled by coal-water slurry gasification, the water-coal-slurry first passes through filter pulp technique Processing again with O2It is obtained by coal-water slurry gasification comprising CO, CO2And H2Water-gas.
- 10. as described in claim 1 a kind of with waste water water-coal-slurry and by the method for water-coal-slurry preparing ethylene glycol, feature exists In: process for separating and purifying described in step (5) includes Deep Cooling Method and pressure-variable adsorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910093099.7A CN109762585A (en) | 2019-01-30 | 2019-01-30 | A method of with waste water water-coal-slurry and passing through water-coal-slurry preparing ethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910093099.7A CN109762585A (en) | 2019-01-30 | 2019-01-30 | A method of with waste water water-coal-slurry and passing through water-coal-slurry preparing ethylene glycol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109762585A true CN109762585A (en) | 2019-05-17 |
Family
ID=66455607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910093099.7A Pending CN109762585A (en) | 2019-01-30 | 2019-01-30 | A method of with waste water water-coal-slurry and passing through water-coal-slurry preparing ethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109762585A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874793A (en) * | 2022-05-09 | 2022-08-09 | 武汉工程大学 | Pulverized coal pyrolysis system capable of realizing rapping ash removal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993344A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing ethylene glycol from synthesis gas |
| CN104229831A (en) * | 2014-08-25 | 2014-12-24 | 中国五环工程有限公司 | Process for preparing synthesis ammonia from synthesis gas and co-producing ethylene glycol |
| CN104531186A (en) * | 2014-12-26 | 2015-04-22 | 西安元创化工科技股份有限公司 | Method for producing tar and hydrocarbon fuel products with coal |
| CN106190327A (en) * | 2016-09-12 | 2016-12-07 | 中国华能集团公司 | A kind of flying dust and the coal gasification of waste water recirculation, cleaning system and method |
-
2019
- 2019-01-30 CN CN201910093099.7A patent/CN109762585A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993344A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing ethylene glycol from synthesis gas |
| CN104229831A (en) * | 2014-08-25 | 2014-12-24 | 中国五环工程有限公司 | Process for preparing synthesis ammonia from synthesis gas and co-producing ethylene glycol |
| CN104531186A (en) * | 2014-12-26 | 2015-04-22 | 西安元创化工科技股份有限公司 | Method for producing tar and hydrocarbon fuel products with coal |
| CN106190327A (en) * | 2016-09-12 | 2016-12-07 | 中国华能集团公司 | A kind of flying dust and the coal gasification of waste water recirculation, cleaning system and method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874793A (en) * | 2022-05-09 | 2022-08-09 | 武汉工程大学 | Pulverized coal pyrolysis system capable of realizing rapping ash removal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bermudez et al. | Production of bio-syngas and bio-hydrogen via gasification | |
| CN104119956B (en) | The hydrogenation methanation method of carbon raw material | |
| CN101959996B (en) | Particulate composition for gasification, preparation and continuous conversion thereof | |
| CN110055104A (en) | A kind of method that the utilization of low-order coal sub-prime prepares natural gas | |
| CN105154121A (en) | Low-rank coal gradation usage poly-generation system and method | |
| CN109652139A (en) | A kind of method and system preparing synthesis gas using volatile matter in low-order coal and waste water | |
| US20200224110A1 (en) | Method of biomass grading pyrolysis gasification in a circulating fluidized bed | |
| CN101979472A (en) | Method for preparing synthesis gas from carbon dioxide serving as pressurized fixed bed gasifying agent instead of water vapor | |
| CN109880654A (en) | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal | |
| Kan et al. | Gasification of biomass | |
| CN109762603A (en) | A method of ammonia is synthesized using low-order coal multipath | |
| CN205133505U (en) | Low order coal grading utilizes many cogeneration system | |
| CN104910969A (en) | Novel brown coal gasification system and method | |
| CN112457168B (en) | Resource treatment method for biodiesel byproduct salt-containing crude glycerol | |
| CN109762585A (en) | A method of with waste water water-coal-slurry and passing through water-coal-slurry preparing ethylene glycol | |
| CN110055107A (en) | A kind of method that low-order coal sub-prime utilizes technique waste water zero-emission | |
| CN110055106B (en) | Method for preparing methanol and oil by poly-generation through low-rank coal quality-based utilization | |
| CN109762612A (en) | A method of using waste water water-coal-slurry and passing through water-coal-slurry methanol | |
| CN102395659A (en) | Method and system for the production of a combustible gas from a fuel | |
| CN109970057A (en) | Cellular activated carbon based on coal liquefaction residue and semi-coke end | |
| CN104531230A (en) | High-efficiency energy-saving water gas purification device | |
| CN110002933B (en) | Method for preparing methanol and low-carbon olefin by poly-generation through low-rank coal quality-based utilization | |
| CN110055105A (en) | A kind of method that low-order coal sub-prime utilizes harmless treatment organic wastewater | |
| CN109762602A (en) | A method of ethylene glycol is prepared using low-order coal multipath | |
| CN110093174A (en) | A kind of method of low-order coal hydrogen manufacturing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190517 |
|
| RJ01 | Rejection of invention patent application after publication |