CN101126035A - Phenol water closed operation high-conversion coal gasification production technique - Google Patents
Phenol water closed operation high-conversion coal gasification production technique Download PDFInfo
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Abstract
A high conversion coal gasification technique by phenol water closed operation comprises gasification agent. The production technique is characterized in that the temperature of the gasification agent is 65-350 DEG C; the water content of the gasification agent is equal to saturation air of the same weight under temperature of 55-60 DEG C. The phenol containing wastewater under the function of pressure pump is atomized and mixed sufficiency with hot air in a mixture box, and then is sent into a gasification furnace to be gasified by an air machine. The phenol containing wastewater refers to a precipitated solution obtained in coal gas cooling process which contains benzene and hydroxybenzene. The wastewater is transported into the oxide layer of the furnace body to be cracked and burned in the completely closed gasification process in a mechanical way without discharging, thus thoroughly solving the problem of phenol water pollution and secondary pollution; meanwhile, part of heat can be reused in furnace to save an amount of coal participating in oxidation reaction, thereby improving gasification efficiency by 3percent-5percent and gasification intensity by more than 10 percent.
Description
Technical field
The invention belongs to coal gasification Technology field, be specifically related to a kind of phenol water closed operation high-conversion coal gasification production technique.
Background technology
As shown in Figure 1, two sections traditional stove refrigerant gas production technique are as follows: pass through transfer mechanism, the coal cinder of appropriate mass and size is sent into coal bunker, also join in the gas furnace uniformly continuously by coal mechanism, in gas furnace, there is the following main chemical reaction of three classes: 1, the reaction between oxygen, the water vapor in carbon in the coal and the vaporized chemical air; 2, the reaction between the oxygen in the vaporized chemical, water vapor, the various generation gas; 3, the heat scission reaction of coal, these three kinds are reflected at the interior different levels of stove and carry out.
Zone of oxidation becomes fire bed again, and thickness is 100～200mm under the normal circumstances.The zone of oxidation significant feature is to make airborne oxygen meet charcoal to carry out rapid thermal chemical reaction, generates a large amount of carbonic acid gas, emits heat simultaneously.The required heat of the thermal chemical reaction of coal gas is kept by this.Fire temperature generally remains on 1100～1250 ℃, is decided by the height of feed coal ash fusion point.
Reducing zone is the zone that generates main inflammable gas, according to the situation that reaction formula carries out, is divided into first reducing zone and second reducing zone (or becoming main reducing zone and time reducing zone).Under the normal circumstances, reducing zone thickness is 200～400mm.The effect of reducing zone is: 1. carbonic acid gas and scorching hot charcoal work, and carry out thermal chemical reaction, generate combustible carbon monoxide; 2. water vapor and scorching hot charcoal carry out endothermic chemical reaction, generate combustible carbon monoxide and hydrogen; 3. except that the reaction of above two classes, secondly also have carbon monoxide and unnecessary steam reaction and produce carbonic acid gas and hydrogen, emit heat simultaneously.
The two-part producer gas divides two sections, and gas in upper segment is left away by the producer top exit, enters electrical tar precipitator and removes tar, and tar flows into the tar jar.Water coolant in the chuck enters steam pockets by vapour pipe.The coal gas that produces enters inter cooler, is left away by the bottom after cooling off, and condensation was separated out poisonous phenol water and flowed into the phenol pond by water pipe after coal gas was cooled; Coal gas enters electro detarrer and removes light oil, and light oil flows into storage tank, and the coal gas after the purification borrows gas exhaust machine to be sent to the user.
Mixture generator coal gas is to adopt air and water vapour gas mixture as vaporized chemical, carries out gasification reaction with carbon and generate inflammable gas in producer.The effect of water vapour is as follows:
(1) absorbs heat because water vapour decomposes, thereby can reduce temperature in the stove.The water yield how much be to control the water yield by control vaporized chemical temperature of saturation.
(2) because water vapour can reduce furnace temperature, be the speed of response of carbon monoxide so weakened the carbon reduction of carbonic acid gas chance, the ratio of carbon monoxide and carbonic acid gas is reduced.
(3) since water vapour in suitable stove under the temperature condition, major part can be decomposed and generated hydrogen and carbon monoxide, so improved the quality of coal gas, the coal gas calorific value is increased.
(4) water vapour can not decompose fully, temperature in the size of rate of decomposition and the stove, coal character, steam vapour amount what etc. factor relevant.Undecomposed water vapour is all sneaked in the coal gas, and flows out producer.Like this since gas furnace to go out temperature higher, thermosteresis is increased, when being with washiness in the coal gas simultaneously, need to purify cooling, otherwise can influence pipeline life-span and user's use, because the coal gas cooling, water displacement is more in pipeline, hinder when serious and normally supply gas, and reduced the thermo-efficiency of user's heating installation.
For above-mentioned reasons, water vapour is all influential to the economy of the quality of the difficulty or ease of normal, the operation of gas production, coal gas and production process.At present, steam vapour amount in the vaporized chemical all adopts the temperature of saturation of mixed gas to control, for example, certain mixed gas station vaporized chemical adopts the gas mixture of air-steam, the size of the water yield is 55～60 ℃ the water yield that saturation steam contained, and the control of the water yield is to be transported to simultaneously in the blending bin at air and water vapor, utilizes the temperature control inductor block, by the temperature of control mixed steam, reach the input of automatic adjustment water vapor." vocational technology " 2006 the 10th phases the 152nd page " analysis of producer gas generator gasification " (Yang Lisen, Wang Diwen) disclose general blast temperature scope at 50～65 ℃, and its disclosed content is quoted at this.
This employing saturated steam process has many advantages, and technology content requires low, and the steam that utilizes recirculated cooling water to produce enters in the stove, and is easy and simple to handle, is easy to control, and the control point is less relatively.
The reason that sewage produces in the gas production process:
The phenol-containing wastewater of gas station mainly contains five kinds of pollution substances (the gas liquor composition is variant in different device parts omitted) such as tar, light oil, crude phenols, ammonia and sulphur, wherein phenols is based on monohydric phenol, the highest with phenol content, secondly p-cresol between also having, it derives from cooling and purifies the washing water in the course of gas and contain the phenol water of condensation, and the growing amount that wherein contains the phenol water of condensation depends on gasification ature of coal and the gasifying process that is adopted.With two sections producer gas station gasification datong bitumites is example, and gas in upper segment is finally cooled off through indirect cooler, and the condensation water quantity of generation is about about the 100kg/t coal, and this water of condensation contains the phenol amount and is about 8500～10000mg/L; The hypomere Coal-gas Washing Water Using contains phenol amount 10mg/L, and water of condensation is along with the increase that recycles the time, and it contains the phenol amount also constantly increases, be increased to a certain degree after, just can influence mass transfer and heat exchange in the device for washing and cooling, thereby bring a series of detrimentally affects.
In decades, how thoroughly to administer phenol-containing wastewater is the environmental protection difficult problem of puzzlement gas station always, the brainstrust of being engaged in the industrial gas design studies is through long term studies and discussion, though groped some effective treatment processs, also obtain certain effect, but still had many weak points.
Several conventional treatment methods of phenol-containing wastewater:
Phenol-containing wastewater processing for gas station generally is divided into two stages: the first, and pretreatment stage, this stage is intended to except that most suspended substances in the decontaminated water and tar etc.; The second, the treatment stage of dephenolize, its objective is most of aldehydes matter in the pretreated sewage and partial organic substances matter are removed.
1.1 pretreatment process: the pretreatment process of having used in gas station generally has following several at present:
1) natural subsidence partition method; 2) mechanical filter method; 3) chemical coagulation-sedimentation method; 4) electro-flotation method; 5) centrifugal separation; 6) add naphtenic acid coke tar refuse absorption method; 7) pressurized dissolved air flotation method; 8) jet air float method
Natural subsidence partition method wherein, can be set directly in the recirculated water process system of gas station, though effect is not very good, but running cost is lower, is adopted as the phenol-containing wastewater pretreatment process by most of gas stations always.Other seven kinds of methods then must be handled in the equipment that is provided with separately, and processing costs is high relatively.
1.2 dephenolization treating method: dephenolization treating method can be divided into physico-chemical processes and biochemical process.
1.2.1 physico-chemical processes
1.2.1.1 steam chemistry dephenolize method
With intensive high-temperature steam heating phenol-containing wastewater, overflowed with steam in the phenol evaporation back in the sewage, and then feed alkali lye and absorb and become sodium phenolate, thereby reach the purpose of dephenolize.This method is simple to operate, invests also lessly, but steam consumption quantity is bigger, and dephenolize efficient is not ideal enough, does not generally reach the purpose of thorough improvement.
1.2.1.2 steam dephenolize method
With the phenol-containing wastewater heating, phenol is evaporated with water vapor, again this part is contained in the phenol steam feeding producer furnace bottom entrained air and use as vaporized chemical, in stove, phenol at high temperature combustion decomposition becomes CO
2And H
2O finally reaches the purpose of dephenolize.Its shortcoming is that it is thing that this method can only remove lower boiling phenol, and energy consumption is bigger, and 1 ton of sewage of every evaporation needs fuel to amount to about 180 kilograms in mark coal approximately, and its shortcoming is that this method is handled phenol-containing wastewater, and energy consumption is big and gas furnace furnace bottom temperature of saturation is wayward.
1.2.1.3 burning method
Phenol-containing wastewater is sprayed into incinerator, make phenol organic matter under the high temperature about 1100 ℃, oxidizing reaction takes place, finally generate CO
2And H
2The O discharging, this method technology is simple, easy to operate, but energy consumption is bigger, and 1 ton of its cost of phenolic wastewater of every burning is about about 200 yuan.At the last century initial stage nineties, the external domestic supporting two stage type gas generating furnace of introducing that reaches all is equipped with phenol water incinerator facility basically, but all on the shelf because of energy consumption problem basically.Be careless manipulation in case utilize burning method to handle another critical defect of phenol-containing wastewater, furnace temperature descends, and tends to cause incomplete combustion, easily forms secondary pollution.
1.2.1.4 solvent extraction dephenolize method
The main technology of this method is divided extraction and desorb two portions, and extraction process is a material redistribution process, utilizes extraction agent that phenol is extracted from sewage; Contain the phenol extraction agent and be in contact with one another with alkali lye again, phenol in the extraction agent and the alkali generation sodium phenolate that reacts, this process is a desorption process.The phenol that water outlet after utilizing this kind dephenolize method to handle still contains 100-200mg/l can not directly discharge, and the loss of extraction agent can cause sewage emulsification, and forms secondary pollution.This method must adopt high efficiency extraction agent and alkali in addition, and running cost is higher.
1.2.1.5 resin dephenolize method
This method main processes comprises absorption and desorb, and the phenol with in the resin absorption waste water carries out desorb with alkali lye then, generates phenol sodium, and this method technological process is comparatively complicated, and it is more to influence the factor of dephenolize efficient, and running cost is higher relatively.
1.2.1.6 sulphonated coal absorption method
This method forms the sodium phenolate dephenolize with the alkali lye absorption then with sulphonated coal polar group absorption phenol, and sulphonated coal absorption is intermittently carried out, and finishing once, circulation comprises the absorption and two links of regenerating.The main drawback of this method is that the suction phenol amount of sulphonated coal is low excessively, and adsorption cycle is too short, the relatively difficulty of resolving, regenerate also.
1.2.1.7 biochemical process
It is culturing micro-organisms that phenol-containing wastewater is carried out biochemical treatment, and utilizes microorganism that the phenol organic matter in the sewage is digested and assimilated to resolve into H
2O and CO
2Process.This method can be divided into aeration, contact oxidation method, bio-disc system and biological filter process etc. again according to the bearing mode of microorganism and the difference of oxygen supply mode.Biochemical process requires comparatively strict to the sewage quality that enters biochemistry pool, organic concentrations such as the coal-tar middle oil and phenol of sewage can not surpass the concentration that microorganism can bear, otherwise, need will just can enter biochemistry pool after the dilution of sewage, so just limited the processing water yield.Microbial acclimation is relatively more difficult simultaneously, and influent concentration exceeds standard, envrionment temperature is not suitable for, and all is easy to the existence of restriction micro-organisms.Northeast factory once adopted biochemical process to handle phenol-containing wastewater, because the conditional request strictness causes its processing cost quite high.
No matter indulge the above, be to burn or biochemical process, and cost is high or cause secondary pollution, and at present numerous gas stations, very the ideal user is extremely rare for phenol water disposal.
Publication number is that the Chinese patent of CN1162624A discloses a kind of process of two stage furnace water gas plant and the processing that contains phenol water, comprise gasification, cooling and purifying and contain phenol water treatment technique, wherein, containing phenol water disposal partly is by containing phenol water pump, the burning thermophore, two sections stoves are formed, containing phenol water is the energy that utilizes the air blowing air, checker brick in the burning thermophore are burnt 800～900 ℃ of high temperature, when lower gasification, spray in the burning thermophore then containing phenol water, carry out heat exchange with checker brick and gasify, enter in two sections stoves the process that produces water-gas with red-hot coke as vaporized chemical then and fall containing phenol water disposal.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, start with from the thermal equilibrium of coal gas generation oxidation and reduction reaction needs, adopt and to burn phenol water in the stove and do not efflux, make coal gas phenol water under the condition of complete closed, move, effectively avoided problem of environmental pollution, and, because the heat that has effectively utilized the burning of coal gas waste heat and phenol to produce, thereby coal changes into the vaporization rate of coal gas and the gasification intensity of gas furnace body of heater unit surface has all had raising.
The following technical scheme of the concrete employing of the present invention:
A kind of phenol water closed operation high-conversion coal gasification production technique comprises vaporized chemical, it is characterized in that, the temperature of described vaporized chemical is greater than 65 ℃, when water content is 55～60 ℃ with the water content of weight saturated air.
The temperature of described vaporized chemical is 65～80 ℃, 80～150 ℃ or 150～250 ℃.
Described vaporized chemical is to contain phenol water to spray in blending bin and enter two sections stoves after warm air mixes.Described hot air temperature is 300～500 ℃.Described warm air is that air carries out entering blending bin after the heat exchange in air cooler, waste heat boiler or gas pipe line.
Beneficial effect of the present invention is: compare with traditional gas furnace gas-made technology, heat exchange has taken place with coal gas of high temperature in the air that enters furnace bottom in heat-exchange equipment, become high temperature air, under the effect of gas blower, be admitted in the blending bin, phenol water is transported in the blending bin by phenol water pump, atomisation unit is arranged in blending bin, atomisation unit with the phenol water atomization after, flass takes place in high temperature air, gasified rapidly, vaporized chemical is undersaturated warm air, and the relative humidity that enters furnace bottom is less, and in traditional technology, add hot steam in the normal temperature air, enter the stokehold and become oversaturated air, portion water will be arranged from the gaseous state liquefy, entering needs to reuptake a large amount of heat gasifications behind the furnace bottom, furnace bottom grieshoch and zone of combustion are caused to a certain degree disadvantageous effect, reduced the calorific value of coal gas.
In this technology, phenolic wastewater moves in the environment of complete closed, obtains cracking and burn in the body of heater zone of oxidation, and is pollution-free; The part heat melts down utilization again, saved the amount that participates in the oxidizing reaction coal, guarantee more coal participation reduction reaction, thereby gasification efficiency improves 3%～5%, gasification intensity improves more than 10%, the phenol water that gets off from the inter cooler condensation is used mechanical mode and all turns back in the burner hearth and burn the environment of complete closed, thoroughly solved phenol water and polluted and secondary pollution problem.
The transformation efficiency height of coal of the present invention: Jincheng coal with calorific value 27000kJ/Kg is an example, the heat that 76%, one kilogram of coal of gasification efficiency slatterns is 6480kJ, if hypomere coal gas is gone into stove from 500 ℃ of heat recuperation that are cooled to 200 ℃, caloric value has 1200kJ approximately, account for 4.4% of one kilogram of coal total heat, account for one kilogram of coal and slattern 18.5% of heat, because technology is successive, energy is in the process of recycling continuously, gasification intensity is improved, and the numerical value of raising can reach 76 theoretically
(1+0.04)%=92%.
Description of drawings
Fig. 1 is a prior art coal gasification production technique schema;
Fig. 2 is a coal gasification production technique schema of the present invention;
Fig. 3 is the equipment flowsheet of embodiment 1;
Fig. 4 is the equipment flowsheet of embodiment 2
Fig. 5 is the equipment flowsheet of embodiment 3
Among the figure, the 1-gas furnace; The 2-gas in upper segment; 3-hypomere coal gas; The 4-cyclone; The 5-electrical tar precipitator; The 6-inter cooler; 7-electric fishing light oil device; 8-coal gas output tube; 9-phenol pond; The 10-heat exchanger; The 11-waste heat boiler; The 12-calorifier; The 13-blending bin; The 14-spraying plant; The 15-steam pockets; The 16-air cooler; 17 is heat exchanger.
Embodiment 1: air carries out entering blending bin after the heat exchange in air cooler.
As the necessary vaporized chemical of producer gas generator---air, under the suction function of blower fan 12, when heat exchanger 10 comes out, become high-temperature gas (300～500 ℃).The poisonous phenol water of discharging from inter cooler 6 is in phenol water pump is transported to blending bin 13, and under the spraying gun 14 blending bin 13 in acted on, phenol water is atomized to become little droplet.The amount of needed water generally is controlled to be the water yield of 55～60 ℃ of saturated airs in the vaporized chemical, and the amount that control adds the phenol water in the blending bin is less than this numerical value, and the part of shortcoming remedies by the steam in the steam pockets 15.Under the effect of high temperature air, droplet is evaporated rapidly at short notice, and be transported to producer gas generator by the hot blast vapour pipe, the temperature that control enters the air of producer gas generator is higher than 65 ℃, and so, the air that enters producer becomes unsaturated air, water is in unit molecule gaseous phase completely, enter in the interior process of the stove furnace bottom grieshoch process, do not have gasification, can not cause the harm such as significantly reduction and inclined to one side stove etc. of grieshoch temperature.
Embodiment 2: waste heat boiler carries out heat exchange process.
From the air that waste heat boiler 11 comes out, become high-temperature gas (300～500 ℃), warm air is transported in the blending bin 13 through heating duct, blower fan 12, and in blending bin 13 under the effect of spraying gun 14, phenol water is atomized to become little droplet.Under the effect of high temperature air, droplet is evaporated rapidly at short notice, and is transported to producer gas generator by the hot blast vapour pipe.
Embodiment 3: transfer lime carries out heat exchange process.
Gas conveying tube is carried out suitable transformation become interchanger 17, hypomere coal gas 3, is passed to heat and its air that drives in the wrong direction, and is heated when out-of-date pneumatic tube by producer 1 centre exit venting.Air links to each other with blower fan 28, under the effect of blower fan, produces pressure reduction between the air ports, and under the effect of pressure, air and coal gas drive in the wrong direction, and by tube wall conduction and radiation effect, coal gas obtains cooling, and air obtains heating.By the heating gas of being lowered the temperature, joining with gas in upper segment enters inter cooler and is further cooled off, and subsequently, enters electric fishing light oil device, purifies the back and borrows gas exhaust machine 13 to be sent to the user.From the air that waste heat boiler comes out, become high-temperature gas (300～500 ℃), warm air is transported in the blending bin through heating duct 29, blower fan 28, and in blending bin under the effect of spraying gun, phenol water is atomized to become little droplet.Under the effect of high temperature air, droplet is evaporated rapidly at short notice, and is transported to producer gas generator by the hot blast vapour pipe.
In traditional technology,, unnecessary heat is diffused in the air, be wasted by air cooler from the waste heat boiler pyritous coal gas that comes out.In this technology, this part heat is melted down utilization again, with respect to having reduced the amount of ginseng as the coal of oxidizing reaction, there is more coal to participate in reduction reaction, generate useful coal gas, vaporization rate can improve 3%～5%, because vaporized chemical adopts warm air to replace air at room temperature, the gasification intensity of coal gas can improve more than 10%, the phenol water that gets off from the inter cooler condensation is used mechanical mode and all turns back in the burner hearth and burn the environment of complete closed, thoroughly solved phenol water and polluted and secondary pollution problem.
Claims (7)
1. a phenol water closed operation high-conversion coal gasification production technique comprises vaporized chemical, it is characterized in that, the temperature of described vaporized chemical is 65～350 ℃, when water content is 55～60 ℃ with the water content of weight saturated air.
2. phenol water closed operation high-conversion coal gasification production technique according to claim 1 is characterized in that, the temperature of described vaporized chemical is 65～80 ℃.
3. phenol water closed operation high-conversion coal gasification production technique according to claim 1 is characterized in that, the temperature of described vaporized chemical is 80～150 ℃.
4. phenol water closed operation high-conversion coal gasification production technique according to claim 1 is characterized in that, the temperature of described vaporized chemical is 150～250 ℃.
5. according to each described phenol water closed operation high-conversion coal gasification production technique in the claim 1 to 4, it is characterized in that, described vaporized chemical be contain that phenol water atomizes in blending bin and with enter vapourizing furnace after warm air mixes.
6. phenol water closed operation high-conversion coal gasification production technique according to claim 5 is characterized in that, described hot air temperature is 300～500 ℃.
7. according to claim 5 or 6 described phenol water closed operation high-conversion coal gasification production techniques, it is characterized in that described warm air is that air carries out entering blending bin after the heat exchange in air cooler, waste heat boiler or gas pipe line.
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Cited By (12)
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| CN101963347A (en) * | 2010-10-19 | 2011-02-02 | 华南理工大学 | Stokehold gas making boiler system |
| CN101974350A (en) * | 2010-08-09 | 2011-02-16 | 高邮市林源科技开发有限公司 | Technological process for producing biomass fuel gas without wastewater discharge by using phenol water gasification and recovery technology |
| CN102041100A (en) * | 2009-10-10 | 2011-05-04 | 华东理工大学 | Method for treating high-concentration organic wastewater |
| CN102515407A (en) * | 2011-12-20 | 2012-06-27 | 太原众联达机械设备有限公司 | Gas station phenol water processing process |
| CN103965970A (en) * | 2013-02-05 | 2014-08-06 | 栾涛 | Treatment method for phenolic water produced by gas producer |
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| DE3310220A1 (en) * | 1983-03-22 | 1984-09-27 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR GASIFYING SOLID FUELS IN THE HIKING BED AND IN THE FLUID BED |
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| CN101963347A (en) * | 2010-10-19 | 2011-02-02 | 华南理工大学 | Stokehold gas making boiler system |
| CN102515407A (en) * | 2011-12-20 | 2012-06-27 | 太原众联达机械设备有限公司 | Gas station phenol water processing process |
| CN103965970B (en) * | 2013-02-05 | 2017-02-15 | 淄博英诺威圣节能科技有限公司 | Treatment method for phenolic water produced by gas producer |
| CN103965970A (en) * | 2013-02-05 | 2014-08-06 | 栾涛 | Treatment method for phenolic water produced by gas producer |
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| CN105018155A (en) * | 2015-08-05 | 2015-11-04 | 华陆工程科技有限责任公司 | Method for producing coal tar and synthesis gas from oil-rich coal through pyrolysis and gasification coupling device and oil gas purification device |
| WO2017032318A1 (en) * | 2015-08-26 | 2017-03-02 | 上海泽玛克敏达机械设备有限公司 | Self-wastewater-treatment environmental gasifier |
| CN107446629A (en) * | 2017-08-31 | 2017-12-08 | 北京神雾电力科技有限公司 | The system and method for handling low-order coal |
| CN110846079A (en) * | 2019-11-20 | 2020-02-28 | 西安交通大学 | Solar-driven lignite poly-generation upgrading system and operation method |
| CN111073709A (en) * | 2019-12-17 | 2020-04-28 | 中国科学院工程热物理研究所 | Energy-saving and emission-reducing system of gas producer |
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