CN112940821B - Method for improving nitrogen fixation efficiency in coal pyrolysis by using coal ash - Google Patents
Method for improving nitrogen fixation efficiency in coal pyrolysis by using coal ash Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010883 coal ash Substances 0.000 title claims abstract description 53
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 16
- 239000000571 coke Substances 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 15
- 230000007613 environmental effect Effects 0.000 abstract 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 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
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- ZXNYKOAICSPUKI-UHFFFAOYSA-N dicyanocyanamide Chemical compound N#CN(C#N)C#N ZXNYKOAICSPUKI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
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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
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/005—After-treatment of coke, e.g. calcination desulfurization
-
- 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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
技术领域technical field
本发明涉及煤热解中氮脱除技术领域，具体涉及一种利用煤灰提高在煤热解中固氮效率的方法。The invention relates to the technical field of nitrogen removal in coal pyrolysis, in particular to a method for improving nitrogen fixation efficiency in coal pyrolysis by utilizing coal ash.
背景技术Background technique
煤在加工利用过程中所产生的污染物现已成为造成生态环境破坏的最大的污染源，在煤热解过程中氮元素以氮氧化物等形式进入空气中，对地球空气污染治理造成了很大的影响。目前针对煤热解产生烟气中氮氧化物的脱除问题，主要依靠如尿素吸收等方法，这类方法存在投资大和需要额外的运行设备等问题。The pollutants produced in the process of coal processing and utilization have now become the largest source of pollution causing damage to the ecological environment. In the process of coal pyrolysis, nitrogen enters the air in the form of nitrogen oxides, which has caused a great deal of air pollution control on the earth. Impact. At present, the removal of nitrogen oxides in flue gas produced by coal pyrolysis mainly relies on methods such as urea absorption. Such methods have problems such as large investment and the need for additional operating equipment.
目前，煤热解烟气中的氮氧化物主要污染来源于氰化氮，在煤炭利用中通过降低氰化氢或者使氰化氢更多地转化为氮气排放，是解决烟气处理方法带来的投资运行费用与占地问题的重要方法。如何简便又高效地降低氰化氢等含氮气体的排放是需要解决的一大问题。At present, the main source of nitrogen oxide pollution in coal pyrolysis flue gas comes from nitrogen cyanide. In coal utilization, by reducing hydrogen cyanide or converting more hydrogen cyanide into nitrogen, it is a solution to the problem of flue gas treatment. It is an important method for the investment and operation cost and land occupation problem. How to easily and efficiently reduce the emission of nitrogen-containing gases such as hydrogen cyanide is a major problem that needs to be solved.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种利用煤灰提高在煤热解中固氮效率的方法，投资少，成本低。The purpose of the present invention is to provide a method for using coal ash to improve the nitrogen fixation efficiency in coal pyrolysis, with low investment and low cost.
为实现上述目的，本发明采用的技术方案如下：一种利用煤灰提高在煤热解中固氮效率的方法，包括：In order to achieve the above object, the technical scheme adopted in the present invention is as follows: a method for utilizing coal ash to improve the nitrogen fixation efficiency in coal pyrolysis, comprising:
(1)将水溶性铁盐和/或水溶性锌盐溶于水中制得处理液，将电厂燃烧后的煤灰浸泡在处理液中30～40min，干燥后备用；(1) Dissolving water-soluble iron salt and/or water-soluble zinc salt in water to prepare a treatment solution, soaking the coal ash after combustion of the power plant in the treatment solution for 30-40min, and drying for later use;
(2)将一定量的原料煤与处理后的煤灰混合并在隔绝空气的情况下进行热解，抑制煤在热解中含氮化合物气体的析出，得到洁净的热解气；(2) Mixing a certain amount of raw coal with the treated coal ash and performing pyrolysis in the absence of air to inhibit the precipitation of nitrogen-containing compound gas during the pyrolysis of coal, and obtain clean pyrolysis gas;
(3)将热解后的半焦或焦炭完全浸泡在酸溶液中1～3h，煤中氮溶出于酸溶液中，浸泡后再洗涤去除掺混在内的煤灰，实现煤中大部分氮的脱除，并得到干净的半焦或焦炭。(3) The pyrolyzed semi-coke or coke is completely immersed in an acid solution for 1 to 3 hours, and the nitrogen in the coal is dissolved in the acid solution, and after immersion, the mixed coal ash is washed and removed, so as to realize the removal of most of the nitrogen in the coal. It is removed and a clean semi-char or coke is obtained.
上述技术方案中，步骤(1)中所述水溶性铁盐为硝酸铁、硫酸铁、氯化铁中的一种或多种，所述水溶性锌盐为硝酸锌、硫酸锌、氯化锌中的一种或多种。In the above technical scheme, the water-soluble iron salt described in step (1) is one or more of ferric nitrate, ferric sulfate, and ferric chloride, and the water-soluble zinc salt is zinc nitrate, zinc sulfate, and zinc chloride one or more of.
上述技术方案中，步骤(1)中所述处理液中的水溶性铁盐和/或水溶性锌盐占煤灰的质量分数为0.1％～0.5％。In the above technical solution, the mass fraction of the water-soluble iron salt and/or the water-soluble zinc salt in the treatment solution in step (1) is 0.1% to 0.5% of the coal ash.
上述技术方案中，步骤(2)中所述煤热解温度为800～1000℃。In the above technical solution, the coal pyrolysis temperature in step (2) is 800-1000°C.
上述技术方案中，步骤(2)中所述处理后煤灰与原料煤的质量比为1：5～10。In the above technical solution, the mass ratio of the treated coal ash to the raw coal in step (2) is 1:5-10.
上述技术方案中，步骤(3)中所述酸溶液为盐酸、硫酸、醋酸、草酸中的一种或多种，所述酸溶液浓度为0.1～0.2mol/L。In the above technical solution, the acid solution in step (3) is one or more of hydrochloric acid, sulfuric acid, acetic acid, and oxalic acid, and the concentration of the acid solution is 0.1-0.2 mol/L.
上述技术方案中，步骤(3)中所述酸溶液与原料煤的质量比为1：10。In the above technical solution, the mass ratio of the acid solution to the raw coal in step (3) is 1:10.
本发明原理如下：煤灰中本身带有氧化铁、氧化铝等氧化物，再经过处理液浸泡处理后，煤灰中更多地增加了如铁等元素的有效成分。在原料煤中掺混处理液处理后的煤灰，煤灰中丰富的物质含有大量阳离子，由于阳离子外电子层比较容易得失电子的特性和较强的氧化性，同时由于各种金属复杂的协同作用，使得处理后的煤灰可以在煤热解过程中起到固定氮和抑制氮氧化物生成的作用，即通过热解时煤中析出的气体，比如HCN、NH3等含氮的气体，与掺混的金属添加助剂发生反应，生成氮化物，同时由于煤灰中本身存在的矿物质和有效成分的协同作用，抑制了HCN、NH3等有害气体的产生从而达到固氮的效果。将热解后的煤再进行洗脱，脱去掺混的煤灰和生成的氮化物。The principle of the invention is as follows: the coal ash itself contains oxides such as iron oxide and alumina, and after being soaked in the treatment liquid, more effective components such as iron are added to the coal ash. The coal ash treated with the treatment liquid is mixed with the raw coal. The rich substances in the coal ash contain a large amount of cations. Because the outer electron layer of the cations is easier to gain and lose electrons and has a strong oxidizing property, and because of the complex synergy of various metals So that the treated coal ash can play the role of fixing nitrogen and inhibiting the formation of nitrogen oxides in the process of coal pyrolysis, that is, the gases precipitated in the coal during pyrolysis, such as HCN, NH 3 and other nitrogen-containing gases, It reacts with the mixed metal additives to form nitrides, and at the same time, due to the synergistic effect of minerals and active ingredients in coal ash, the generation of harmful gases such as HCN and NH 3 is inhibited to achieve the effect of nitrogen fixation. The pyrolyzed coal is eluted again to remove the mixed coal ash and the generated nitrides.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1)煤中氮脱除效率高：采用处理液处理过的煤灰掺混热解煤可以有效降低热解气中含氮气体的排放；1) High nitrogen removal efficiency from coal: the coal ash treated with the treatment liquid mixed with pyrolysis coal can effectively reduce the emission of nitrogen-containing gas in the pyrolysis gas;
2)对煤热解后的热解气利用过程影响小：采用处理液处理后煤灰掺混可以在煤热解中减少有害含氮气体的排放，对处理煤热解气体的后续装置的压力有所减小；2) Small influence on the utilization process of the pyrolysis gas after coal pyrolysis: the blending of coal ash after treatment with the treatment liquid can reduce the emission of harmful nitrogen-containing gases in the coal pyrolysis, and reduce the pressure on the subsequent equipment for processing the coal pyrolysis gas. reduced;
3)技术方法可应用性广泛：采用处理后的煤灰掺混的同时，可以同搭配相对应的固硫脱硫类形的添加助剂同时使用，一举多得，减少生产工序，普适性强；3) The technical method has a wide range of applicability: when the treated coal ash is used for blending, it can be used together with the corresponding additives of solid sulfur and desulfurization type. ;
4)需要用到的成分容易获取：本发明所用煤灰是电厂燃烧后废弃的煤灰，其中含有大量的矿物和自然的金属氧化物，为固体废弃物煤灰再利用提供了一条新思路。同时本发明在实际操作中，在现有的热解制备半焦的过程中引入湿式选煤的方法，只需在选煤中加入酸洗过程，固定完成氮的处理后的煤灰会随着酸洗液而脱除于煤中，无需更多的额外工序即可实现，方法简单，成熟有效。4) The components to be used are easy to obtain: the coal ash used in the present invention is the coal ash discarded after combustion in the power plant, which contains a large amount of minerals and natural metal oxides, which provides a new idea for the reuse of solid waste coal ash. At the same time, in the actual operation of the present invention, the method of wet coal preparation is introduced into the existing process of preparing semi-coke by pyrolysis, and it is only necessary to add an acid washing process to the coal preparation, and the coal ash after fixing the nitrogen treatment will follow The pickling solution is removed from the coal, which can be realized without more additional processes. The method is simple, mature and effective.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步详细说明。The present invention will be further described in detail below in conjunction with specific embodiments.
在原料煤中加入处理液处理后的煤灰，所述处理液所含的添加物质为水溶性铁盐和/或水溶性锌盐，将所述处理液处理后的煤灰与原料煤以1：5～10的质量比混合，将混合后的煤样放入高温管式炉中，在隔绝空气的情况下进行热解，煤热解温度为800～1000℃。The coal ash treated with the treatment solution is added to the raw coal, and the added substances contained in the treatment solution are water-soluble iron salts and/or water-soluble zinc salts. : 5～10 mass ratio mixing, put the mixed coal sample into a high temperature tube furnace, and carry out pyrolysis under the condition of isolating air, and the coal pyrolysis temperature is 800～1000℃.
将煤热解过的半焦通过酸溶液酸洗脱除掺混的煤灰和其固定下来的氮化物，从而提高氮脱除效率。所述酸包括盐酸、硫酸、醋酸、草酸中的任一种或几种混合物。所述酸溶液浓度为0.1～0.2mol/L。所述酸溶液与原料煤的质量比为1：10。所述酸溶液浸洗时间为1～3h。将酸洗过的煤样通过大量的水进行水洗，从而脱去煤中引入的杂质离子。The coal-pyrolyzed semi-coke is acid-eluted with an acid solution to remove the mixed coal ash and its fixed nitrides, thereby improving the nitrogen removal efficiency. The acid includes any one or a mixture of hydrochloric acid, sulfuric acid, acetic acid and oxalic acid. The concentration of the acid solution is 0.1-0.2 mol/L. The mass ratio of the acid solution to the raw coal is 1:10. The acid solution soaking time is 1-3h. The acid-washed coal sample is washed with a large amount of water to remove the impurity ions introduced in the coal.
本发明所获得煤焦可作为民用燃料或煤气化、液化原料。The char obtained by the invention can be used as civil fuel or raw material for coal gasification and liquefaction.
实施例1Example 1
取电厂燃烧后的煤灰，按煤灰0.5％的质量分数称取硝酸铁并溶于适量自来水中，制得处理液。将煤灰置于处理液中浸泡40min后干燥。热解的原料煤全氮含量0.59％、粒度小于0.15mm。将原料煤与处理后的煤灰按5：1的质量比均匀混合。用瓷舟承载2g处理过的煤样，将瓷舟放入高温管式炉中并在隔绝空气的情况下进行热解，热解终温度为800℃，并在终温停留30min。配制0.1mol/L的草酸溶液，草酸溶液与原料煤质量比为1：10，并将热解后的煤样浸入其中浸泡2h。将浸泡过的煤样进行三轮水洗，每次水洗10min。热解结果表明，烟气中氮元素含量由占原料煤全氮含量的23.3％降低至2.8％，其固氮率为87.9％。Take the coal ash after combustion in the power plant, weigh ferric nitrate according to the mass fraction of 0.5% of the coal ash, and dissolve it in an appropriate amount of tap water to prepare a treatment solution. The coal ash was soaked in the treatment solution for 40 min and then dried. The total nitrogen content of the pyrolyzed raw coal is 0.59% and the particle size is less than 0.15mm. The raw coal and the treated coal ash are uniformly mixed in a mass ratio of 5:1. A porcelain boat was used to carry 2 g of the treated coal sample, and the porcelain boat was placed in a high-temperature tube furnace and pyrolyzed in the absence of air. The final pyrolysis temperature was 800 °C, and the final temperature was held for 30 min. Prepare 0.1mol/L oxalic acid solution, the mass ratio of oxalic acid solution and raw coal is 1:10, and immerse the coal sample after pyrolysis in it for 2 hours. The soaked coal samples were washed with three rounds of water for 10 min each time. The pyrolysis results showed that the nitrogen content in the flue gas decreased from 23.3% of the total nitrogen content of the raw coal to 2.8%, and the nitrogen fixation rate was 87.9%.
实施例2Example 2
取电厂燃烧后的煤灰，按煤灰0.4％的质量分数称取硝酸锌并溶于适量洁净的工业用水中，制得处理液。将煤灰置于处理液中浸泡30min后干燥，热解的原料煤全氮含量0.51％、粒度小于0.15mm。将原料煤与处理后的煤灰按10：1的质量比均匀混合，同时添加有利于固硫的金属添加剂。用瓷舟承载3g处理过的煤样，将瓷舟放入高温管式炉中并在隔绝空气的情况下进行热解，热解终温为900℃，并在终温处停留30min。配制0.1mol/L的盐酸溶液，盐酸溶液与原料煤质量比为1：10，并将热解后的煤样浸入其中浸泡3h。将浸泡过的煤样进行三轮水洗，每次水洗10min。热解结果表明，烟气中的氮元素含量由占原料煤全氮含量的22.3％降低至2.1％，其固氮率为90.6％，同时硫元素在烟气中含量也有所下降。The coal ash after combustion in the power plant is taken, and the zinc nitrate is weighed according to the mass fraction of 0.4% of the coal ash and dissolved in an appropriate amount of clean industrial water to prepare a treatment solution. The coal ash is soaked in the treatment solution for 30 minutes and then dried. The total nitrogen content of the pyrolyzed raw coal is 0.51% and the particle size is less than 0.15mm. The raw coal and the treated coal ash are uniformly mixed in a mass ratio of 10:1, and a metal additive that is beneficial to sulfur fixation is added at the same time. A porcelain boat was used to carry 3 g of the treated coal samples, and the porcelain boat was placed in a high-temperature tube furnace and pyrolyzed in the absence of air. The final pyrolysis temperature was 900 °C, and the final temperature was held for 30 min. Prepare 0.1mol/L hydrochloric acid solution, the mass ratio of hydrochloric acid solution to raw coal is 1:10, and immerse the coal sample after pyrolysis in it for 3 hours. The soaked coal samples were washed with three rounds of water for 10 min each time. The pyrolysis results showed that the nitrogen content in the flue gas decreased from 22.3% of the total nitrogen content of the raw coal to 2.1%, and the nitrogen fixation rate was 90.6%. At the same time, the content of sulfur in the flue gas also decreased.
实施例3Example 3
取电厂燃烧后的煤灰，按煤灰0.5％的质量分数称取硫酸铁并溶于适量去离子水中，制得处理液。将煤灰置于处理液中浸泡30min后干燥。热解的原料煤全氮含量0.45％、粒度小于0.15mm。将原料煤与处理后的煤灰按10：1的质量比均匀混合。用瓷舟承载2g处理过的煤样，将瓷舟放入高温管式炉中并在隔绝空气的情况下进行热解，热解终温度为1000℃，并在终温停留30min。配制0.2mol/L的醋酸溶液，醋酸溶液与原料煤质量比为1：10，并将热解后的煤样浸入其中浸泡1h。热解结果表明，烟气中氮元素含量由占原料煤全氮含量的22.1％降低至2.2％，其固氮率为81.1％。Take the coal ash after combustion in the power plant, weigh ferric sulfate according to the mass fraction of 0.5% of the coal ash, and dissolve it in an appropriate amount of deionized water to prepare a treatment solution. The coal ash was soaked in the treatment solution for 30 minutes and then dried. The total nitrogen content of the pyrolyzed raw coal is 0.45% and the particle size is less than 0.15mm. The raw coal and the treated coal ash are uniformly mixed in a mass ratio of 10:1. A porcelain boat was used to carry 2 g of the treated coal sample, and the porcelain boat was placed in a high-temperature tube furnace and pyrolyzed in the absence of air. The final pyrolysis temperature was 1000 °C, and the final temperature was held for 30 min. Prepare 0.2mol/L acetic acid solution, the mass ratio of acetic acid solution and raw coal is 1:10, and immerse the coal sample after pyrolysis in it for 1 hour. The pyrolysis results showed that the nitrogen content in the flue gas decreased from 22.1% of the total nitrogen content of the raw coal to 2.2%, and the nitrogen fixation rate was 81.1%.
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