CN100593509C - Method for producing synthesis gas by using slime containing carbon-hydrogen substance - Google Patents

Method for producing synthesis gas by using slime containing carbon-hydrogen substance Download PDF

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CN100593509C
CN100593509C CN 200810132975 CN200810132975A CN100593509C CN 100593509 C CN100593509 C CN 100593509C CN 200810132975 CN200810132975 CN 200810132975 CN 200810132975 A CN200810132975 A CN 200810132975A CN 100593509 C CN100593509 C CN 100593509C
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gas
temperature
thin
buck
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CN101407313A (en
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门长贵
郑化安
刘国平
张勇
贺根良
徐红东
韦孙昌
徐宏伟
李璞
薛薇
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Xi'an Origin Chemical Technologies Co., Ltd.
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NORTHWEST RESEARCH INSTITUTE OF CHEMICAL INDUSTRY
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Abstract

The invention discloses a method for producing synthesis gas by using slurries containing hydrocarbon matter. The method comprises the following six parts of: the preparation of the slurries containing the hydrocarbon matter, the pressurization high-temperature gasification of slurries containing the hydrocarbon matter, the cooling and ash removal by bubbling water-bath temperature-reduction of high-temperature crude synthesis gas, the temperature-reduction dust removal and washing purification of the crude synthesis gas, the discharging of the crude ash, and the processing of the water containing fine ash. The method is not only applicable to the pressurization high-temperature gasification of solid-state or liquid-state hydrocarbon matter, but also applicable to the pressurization high-temperature gasification of the mixture of various solid-state and/or liquid-state hydrocarbon matters simultaneously. The method has good gasification index, simple device, less investment and convenient operation, is easy for upsizing, and has the positive effects of being wide in the applicable range of raw materials, being environment friendly and the like.

Description

A kind of method of using producing synthesis gas from hydrocarbon substance-containing slurry
[technical field]
The present invention relates to a kind of technical field of resource reutilization, more specifically, the present invention relates to utilize contain the method that hydrocarbon solid-state and/or fluent meterial prepares synthetic gas.
[background technology]
As everyone knows, the energy is the important substance basis that social sustainable development was depended on and promoted to human society for existence, and in world's fossil energy reserves, oil, Sweet natural gas and coal etc. contain hydrocarbon material and account for sizable ratio.In the energy structure of China, coal accounts for about 70% (weight), realizes that the cleaning of coal, the efficient utilization have great reality and strategic importance.Because the China's oil resource is fewer, technology with gelatin liquefaction system oil belongs to the state key supporting technology, development in recent years rapidly, the transformation efficiency of technology of gelatin liquefaction system oil own is not high simultaneously, produce and a large amount of contain hydrocarbon solid-state (or liquid) material, and these a large amount of hydrocarbon solid-state (or liquid) materials that contain are badly in need of utilizing again.The present invention is primarily aimed at one or more pressurized high-temperature gasifications that contains hydrocarbon solid-state (or liquid) material (coal, petroleum pitch, coal liquefaction residue, refinery coke, biomass, municipal wastes, organic waste residues, residual oil, various waste oil).
Gasification technology is through constantly development is perfect, and entrained flow bed gasification technology is good owing to its gasification index, efficient energy-saving, the obvious favor that is subjected to numerous manufacturers of environmental benefit.Entrained flow bed gasification technology has dry method pressurized gasification technology and wet method pressurized gasification technology at present, the dry method gasification index is better, cold gas efficiency is higher, but plant investment is huge, moreover do not have the heavy industrialization device to produce the synthetic gas experience, the shell dry method gasification installation of domestic present introduction all is in the stage of fumbling.The wet method gasification mainly is about the coal slurry gasification of concentration 60% (weight)～65% (weight), because it is convenient that coal slurry prepares, carries, measures, controls, be easy to realize high-pressure gasified, equipment domesticizes substantially, plant investment is lower, domestic at present existing number man is in normal operation, but the wet method gasification has certain selection to the ash fusion point of coal, ash oontent etc.
For example CN 1260326C discloses a kind of pressurized gasifying process of polynary slurry, and this technology comprises polynary slurry preparation, pressurized gasification, raw gas purifying, lime-ash discharging and grey water handing five parts.
The present invention is directed to domestic Energy Situation, contain hydrocarbon solid-state (or liquid) reluctant situation of material in a large number, on the basis of carrying out a large amount of research work, made the present invention in the face of what form after the Coal Liquefaction Project.In order to make full use of secondary resource, adopt one or more to contain hydrocarbon solid-state (or liquid) material and produce concentration and carry out the high-temperature pressurizing entrained flow gasification at 58～80% (weight), mobile well hydrocarbon substance-containing slurry, generate with CO, H 2And CO 2Be synthetic gas, reducing gas or the fuel gas of main ingredient, thereby realize containing effective utilization of hydrocarbon solid-state (or liquid) material, various organic waste water and spent pulping liquor (can be used as preparation hydrocarbon substance-containing slurry water).Because hydrocarbon substance-containing slurry is dense, be convenient to high-temperature operation, and the vaporized chemical consumption is lower, cold gas efficiency is higher, the feed stock conversion height, and gasification index is better.
[summary of the invention]
[technical problem that will solve]
The purpose of this invention is to provide a kind of method of using producing synthesis gas from hydrocarbon substance-containing slurry, this method has the raw material wide accommodation, and gasification index is good, the process unit less investment, be easy to maximize, easy to operate and eco-friendly characteristics are comprehensive utilization of energy technology of a kind of excellence.
[technical scheme]
The object of the present invention is achieved like this: this method comprises the hydrocarbon substance-containing slurry preparation, the gasification of hydrocarbon substance-containing slurry pressurized high-temperature, the cooling of high temperature crude synthesis gas, bubbling water-bath cooling remove lime-ash, crude synthesis gas cooling dedusting, washing, purifying, cinder slag discharging and contain six parts of thin grey water handing.
Various piece is described below, promptly following each step respectively:
The preparation of A, hydrocarbon substance-containing slurry: one or more solid-state and/or liquid hydrocarbon material, water, auxiliary agent and additive aqueous mixtures of containing are sent into grinding machine 1 and ground, prepare the slip that contains hydrocarbon material;
The pressurized high-temperature gasification of B, hydrocarbon substance-containing slurry: the hydrocarbon substance-containing slurry that allows above-mentioned steps A obtain enters in the reaction chamber of this reactor 11 by three runner spraying guns 30 in interior heat preserving type air-flow bed coal-gasification reactor 11 upper ends, under the condition of 1250 ℃～1500 ℃ of temperature and pressure 0.1～10MPa, carry out violent incomplete combustion reaction, generate and contain CO, H with vaporized chemical from pipeline 23 2And CO 2The high temperature crude synthesis gas of main ingredient and the mixture of high-temperature ash.
Described three runner spraying guns 30 are a kind of telescoping structures, it is made up of centre channel 63, interior ring passage 64 and outer ring channel 65, described centre channel 63 and outer ring channel 65 are vaporized chemical passages, ring passage 64 is hydrocarbon substance-containing slurry passages in described, described hydrocarbon substance-containing slurry and described vaporized chemical carry out thorough mixing in three runner spraying guns, 30 exits and are well atomized, the atomizing flow field of formation and interior heat preserving type air-flow bed coal-gasification reactor 11 reaction chambers coupling.
Heat preserving type air-flow bed coal-gasification reactor 11 is cylindrical tubes in described, the top of this reactor 11 is reaction chamber, the bottom is a cooling room, its reaction chamber is interior heat-preserved and heat-insulated, wash away the erosive material and make with standing high-temperature ash near the internal layer of reaction chamber, the middle layer is to have used heat-blocking action, prevents that the material of calorific loss from making, skin near reactor 11 housings is to use to play insulation effect, and the material of reduction case temperature is made; Described cooling room is provided with water coolant sparger 34, telescopic inner core 31 and urceolus 32, and inner core 31 upper ends and water coolant sparger 34 are connected and fixed, and urceolus 32 is supported on the cooling room housing, adopts preset pieces to fix between the inner/outer tube 31,32.
C, the cooling of high temperature crude synthesis gas, bubbling water-bath cooling removes lime-ash: the high temperature crude synthesis gas and the high-temperature ash mixture that allow above-mentioned steps B obtain mix with the water coolant that enters described reactor 11 cooling rooms by described water coolant sparger 34, then, inner core 31 by described cooling room enters the bubbling water-bath 33 that is arranged in these reactor 11 cooling room bottoms, through water quench, after bubbling water-bath 33 coolings remove lime-ash, the cinder slag is trapped in the bottom, the crude synthesis gas that contains a small amount of thin ash rises along the annular space between inner core 31 and the urceolus 32, increase owing to the space in the annular space exit suddenly, gas velocity significantly reduces, portion of water of carrying secretly in the crude synthesis gas and ash content are got back to bottom bubbling water-bath 33, and gas flows out described reactor 11 along outlet conduit 12.
D, cinder slag discharging: allow the cinder slag after water quench, bubbling water-bath 33 coolings remove lime-ash from above-mentioned steps C enter bottom cinder slag blowdown system, the cinder slag enters lock hopper 24 by lock slag valve 22, discharge by vent valves 25, the water in the cinder slag enters the vacuum evaporator 44 that contains thin grey water handing part.
E, crude synthesis gas cooling dedusting, washing, purifying: will or enter from the crude synthesis gas that contains a small amount of thin ash of above-mentioned steps C and remove the thin buck of wherein carrying secretly that contains in the air water separator 13, the thin buck of collecting that contains is sent to along pipeline 28 after reducing pressure and is carried out thin grey water handing, delivers to gas-water mixer 15 and remove the crude synthesis gas that contains thin buck along pipeline 14; Perhaps will directly deliver to gas-water mixer 15 without air water separator 13 from the crude synthesis gas that contains a small amount of thin ash of step C along pipeline 12; In gas-water mixer 15, this crude synthesis gas enters grey water-circulating pump 19 and arrives the buck thorough mixing of gas-water mixers 15 through grey water-circulating pump 19 pressure-raisings along pipeline 20 with returning from gas wash tower 17 bottom bubbling style water-bath storage tanks 41 along pipeline 18, crude synthesis gas then, water enters gas wash tower 17 with the mixture of a small amount of thin ash by pipeline 16, arrive bubbling style water-bath storage tank 41 by downtake 39 and wash ash, rise by the annular space of upcast 40 then with downtake 39, by eddy flow plate 38 and traverse baffle 37, tower tray 36 carries out multistage washing, and 26 discharges obtain synthetic gas from gas wash tower 17 tops along pipeline after scum dredger 35 foam removals separate; The buck of bubbling style water-bath storage tank 41 is divided into two-way behind grey water-circulating pump 19 pressure-raisings, one curb pipeline 20 is sent into the thin ash that gas-water mixer 15 soaks in the crude synthesis gas, and the water coolant sparger 34 of heat preserving type air flow bed reactor 11 cinder notch below was as water coolant in another curb pipeline 21 was sent into.
F, contain thin grey water handing: these gas wash tower 17 bubbling style water-bath storage tanks 41 bottoms contain thin buck and contain thin buck and contain thin grey water handing along pipeline 28, the thin buck that contains of discharging from the cooling room of reactor 11 after pipeline 29 reduces pressure respectively along pipeline 27, air water separator 13 are isolating, at first enter high-temperature water heater's 42 step-downs, the step-down escaping gas enters grey water-to-water heat exchanger 57 or reclaims hot-water tower 60 and reclaim heat; Concentrated after high-temperature water heater's 42 step-downs contains thin buck and enters low-temperature water heating device 43 and carry out step-down once more, escaping gas or directly enter degassing tank 55 as thermal source after the step-down is perhaps by entering de aerated water groove 55 as thermal source after the condenser 59 heat exchange cooling; These low-temperature water heating device 43 bottoms concentrate and to contain thin buck and enter vacuum evaporator 44 and carry out step-down, and vacuum evaporator 44 also receives the pulp water of cinder slag discharge unit simultaneously; Escaping gas enters negative pressure separator 46 after the 58 cooling coolings of negative pressure condenser in vacuum evaporator 44, enter off-gas pump 47 after separating moisture, emptying after off-gas pump separator 48 separates moisture again, off-gas pump separator 48 isolating water and negative pressure separator 46 isolating water flow into aqua storage tanks 52, and vacuum evaporator 44 bottoms concentrate and contain thin buck enter clarifying tank 50 behind clarifying tank feeding pump 49 pressure-raisings; Add flocculation agent and make thin grey suspended substance flocculating settling in clarifying tank 50, the top overflow water flows into aqua storage tank 52, and all flow into buck part behind grey water pump 54 pressure-raisings of aqua storage tank 52 and send into degassing tank 55, and a part is as wash-down water, and small part effluxes; In degassing tank 55, the gas dissolved of carrying secretly in circulation buck emptying after heating adds dispersion agent at degassing tank 55 water outlets or in degassing tank 55, simultaneously to alleviate the fouling of interchanger and ash-water pipeline; The circulation buck enters grey water-to-water heat exchanger 57 or reclaims hot-water tower 60 through degassing water pump 56 pressure-raisings, and sends into gas wash tower 17 middle and lower part imports after high-temperature water heater's 42 escaping gas heat exchange temperature raisings, arrives bubbling style water-bath storage tank 41 and recycles; Higher concentrated of clarifying tank 50 bottom ash contents contains thin buck and enters vacuum band-type filter machine 51 through filter feeding pump 53 pressure-raisings, and with thin ash and water sepn, thin ash is collected the back discharge vacuum band-type filter machine 51 in, and isolated water comes back in the clarifying tank 50.
In the present invention, describedly contain that hydrocarbon material is selected from solid carbon-contg hydrogen material and/or liquid state contains hydrocarbon material; Described solid carbon-contg hydrogen material is one or more solid carbon-contg hydrogen materials that are selected from coal, petroleum pitch, coal liquefaction residue, refinery coke, biomass, municipal wastes, organic waste residues; It is that one or more are selected from residual oil, waste oil, the liquid state that contains hydrocarbon organic waste water, spent pulping liquor contains hydrocarbon material that described liquid state contains hydrocarbon material.
Described vaporized chemical is selected from air, oxygen rich gas or pure oxygen.Described oxygen rich gas is that oxygen and one or more are selected from the mixture of the gas of nitrogen, argon gas, carbonic acid gas, and wherein oxygen content is in this gaseous mixture cumulative volume 〉=90%.Described vaporized chemical is pure oxygen or oxygen rich gas preferably, more preferably pure oxygen.
Described auxiliary agent is that one or more are selected from CaCO 3Wingdale, the FeSO of content 〉=95% (weight) 4, K 2CO 3, Na 2CO 3, ammoniacal liquor or caustic soda auxiliary agent, CaCO preferably 3Wingdale, the FeSO of content 〉=95% (weight) 4And caustic soda, be more preferably CaCO 3The Wingdale and the caustic soda of content 〉=95% (weight).
Described additive is one or more additives that are selected from sodium lignosulfonate, calcium lignin sulphonate, polycondensation sodium naphthalene sulfonate, high polymerization sodium naphthalene sulfonate or non-gelationus high phosphorus china clay, preferably sodium lignosulfonate, calcium lignin sulphonate, polycondensation sodium naphthalene sulfonate or non-gelationus high phosphorus china clay are more preferably sodium lignosulfonate or non-gelationus high phosphorus china clay.
The described ratio that contains hydrocarbon material, water, auxiliary agent and additive is respectively in its material gross weight 56～80%, 18～40%, 0～4%, 0.2～0.4%.
In the present invention, described interior heat preserving type air-flow bed coal-gasification reactor 11 is a cylindrical tube or truncated cone cylindrical shell, and its cylindrical shell height is 4 to 5 with the ratio of mean diameter.Preferably 4 to 4.8, be more preferably 4 to 4.5.
Heat preserving type air flow bed reactor 11 is provided with direct or indirect temperature measuring equipment in described, wherein the direct temperature measurement device is to insert pyrometer couple in reaction chamber, the front end of this thermopair with concordant near the reaction chamber inner layer material or in the 10～20mm that contracts, directly measure reaction chamber temperature; Temperature measuring equipment is to use pyrometer couple to detect casing surface temperature indirectly, judges the operation conditions of this reactor 11.
Described gas-water mixer 15 is made up of outer tube and center-aisle, center-aisle is a kind of throat tubular construction, crude synthesis gas enters from outer tube, the middle standpipe tube passage is walked buck, return by pipeline 18 by gas wash tower 17 bottom bubbling style water-bath storage tanks 41 in the trunnion exit and to enter grey water-circulating pump 19 and even along buck and crude synthesis gas thorough mixing that pipeline 20 arrives gas-water mixers 15, the thin ash in the crude synthesis gas is soaked into fully through grey water-circulating pump 19 pressure-raisings.
Described gas wash tower 17 is cylindrical overpressure resistant barrels, and the middle part of going up of this washing tower is provided with scum dredger 35, tower tray 36 and traverse baffle 37, eddy flow plate 38, and the bottom is provided with gas downtake 39, upcast 40 and bubbling style water-bath storage tank 41.
Contain in the thin grey water handing described, the recovery heat is or allows the step-down escaping gas enter grey water-to-water heat exchanger 57 indirect heat exchanges, in grey water-to-water heat exchanger 57 to from the circulation buck heating of degassing tank 55 behind degassing water pump 56 pressure-raisings, after being condensed into liquid state, step-down effusion gas major part enters air water separator 45, its gas is discharged burning emptying or recycling from air water separator 45 tops, isolated water is got back to degassing tank 55; Perhaps allow the step-down escaping gas enter and reclaim hot-water tower 60 direct heat exchanges, in reclaiming hot-water tower 60 to from the circulation buck heat temperature raising of degassing tank 55 through water pump 56 pressure-raisings that outgas, the back small portion gas of self lowering the temperature is dissolved in the circulation buck again, return gas wash tower 17 middle and lower part imports behind pressure-raising pump 61 pressure-raisings, most of gas is discharged burning or is recycled from the top.
Below in conjunction with Figure of description method of the present invention will be described in more detail.
Fig. 1,2, the 3rd, process flow sheet of the present invention.
At first; select for use from one or more of stock yard and contain hydrocarbon solid-state and/or fluent meterial; coal for example; petroleum pitch; coal liquefaction residue; refinery coke; biomass; municipal wastes; organic waste residues; residual oil; mixtures such as various waste oil; after protecting grinding machine to remove the iron that may exist in the solid carbon-contg hydrogen material with magnet; be crushed to granularity again less than 30mm; deliver to grinding machine 1 import through travelling belt; with water; contain hydrocarbon organic waste water comprising various; spent pulping liquor; auxiliary agent; the additive aqueous solution carries out mixed grinding according to described ratio, makes hydrocarbon substance-containing slurry.
The described broken crusher that uses is normally used in the art crusher, for example the crusher sold with the impact breaker trade(brand)name with impact breaker trade(brand)name or mining and metallurgy company of great Santex Group with impact breaker trade(brand)name, machine Manufacturing Co., Ltd of Shanghai generation nation of Shanghai magnificent machinofacture far away company limited; Described grinding machine is normally used in the art grinding machine, for example: the grinding machine that Jiangsu Jiangyin Yate Machinery Manufacturing Co., Ltd. sells with the ball mill trade(brand)name with rod mill trade(brand)name or Shenyang Nonferrous Metallurgical Machinery Plant company with rod mill trade(brand)name, Shenyang Heavy Machinery Group Limited Liability Company.
Different according to material performance and kind, can select rational grinding body gradation is that ball mill is selected rational steel ball matching, rod mill is selected rational frotton proportioning, so that the rational size distribution in the hydrocarbon substance-containing slurry, various granularities are filled mutually, fully improve hydrocarbon substance-containing slurry concentration.
Generally speaking, the size-grade distribution in its hydrocarbon substance-containing slurry is as follows:
Figure C20081013297500131
All pulping raw materials can adopt the automatic or manual metering outfit to measure, solid material generally adopts Weighing, generally employing amount of liquid starting material volume metering, can guarantee the stable of each component concentration like this, be convenient to prepare qualified hydrocarbon substance-containing slurry, carry out so that gasification operation can be stablized.
In order to make hydrocarbon substance-containing slurry under the situation of higher concentration, have good rheological, be easy to pumping, need make used additives and additive.
On meaning of the present invention, described auxiliary agent should be appreciated that it is to have the agent that reduces ash fusion point and regulate the pH value effect.Described auxiliary agent is that one or more are selected from CaCO 3Wingdale, the FeSO of content 〉=95% (weight) 4, K 2CO 3, Na 2CO 3, ammoniacal liquor or caustic soda auxiliary agent, CaCO preferably 3Wingdale, the FeSO of content 〉=95% (weight) 4And caustic soda, be more preferably CaCO 3The Wingdale and the caustic soda of content 〉=95% (weight).The usage quantity of its auxiliary agent generally is in hydrocarbon substance-containing slurry gross weight 0～4%; Preferably 0.01～2%; Be more preferably 0.1～1%.
Described additive should be appreciated that it is the agent with dispersion and stabilization.Described additive is one or more additives that are selected from sodium lignosulfonate, calcium lignin sulphonate, polycondensation sodium naphthalene sulfonate, high polymerization sodium naphthalene sulfonate or non-gelationus high phosphorus china clay, preferably sodium lignosulfonate, calcium lignin sulphonate, polycondensation sodium naphthalene sulfonate or non-gelationus high phosphorus china clay are more preferably sodium lignosulfonate or non-gelationus high phosphorus china clay.The usage quantity of its additive generally is in hydrocarbon substance-containing slurry gross weight 0.2-0.4%; 0.25-0.37% preferably; Be more preferably 0.30-0.35%.
The hydrocarbon substance-containing slurry of above-mentioned preparation enters in the hydrocarbon substance-containing slurry medial launder 3 through pipeline 2 gravity flows, send into low pressure hydrocarbon substance-containing slurry pump 4 by pipeline, behind low pressure hydrocarbon substance-containing slurry pump 4 pressure-raisings, send in the hydrocarbon substance-containing slurry storage tank 6 along pipeline 5.Described low pressure hydrocarbon substance-containing slurry pump 4 is a kind of diaphragm pistonpumps, for example the pump sold with Geho pump trade(brand)name with Feluwa pumpen trade(brand)name or Geho pump Holthuis B.V company with diaphragm pistonpump trade(brand)name, the intelligent merchant's engineering equipment in Shanghai company limited of Shenyang Nonferrous Metallurgical Machinery Plant company.In order to prevent that the hydrocarbon substance-containing slurry precipitation from causing line clogging and making hydrocarbon substance-containing slurry uniform and stable, is provided with agitator at hydrocarbon substance-containing slurry medial launder 3 and hydrocarbon substance-containing slurry storage tank 6.Described agitator is normally used in the art mechanical stirrer, for example three propeller agitators or quaterfoil formula agitator.
Then, hydrocarbon substance-containing slurry in hydrocarbon substance-containing slurry storage tank 6 enters high pressure hydrocarbon substance-containing slurry pump 8 by pipeline 7, heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying guns 30 in behind high pressure hydrocarbon substance-containing slurry pump 8 pressure-raisings, the high pressure hydrocarbon substance-containing slurry of constant pressure being sent into along pipeline 9, three runner spraying guns 30 are installed by top installing port 10, top installing port 10 is implemented fixing to three runner spraying guns 30 simultaneously, described hydrocarbon substance-containing slurry with atomize at three runner spraying guns, 30 exit thorough mixing and by vaporized chemical from the vaporized chemical of pipeline 23, simultaneously in pressurization, violent incomplete combustion reaction takes place under the hot conditions, generates with CO, H 2And CO 2High temperature crude synthesis gas and high-temperature ash for main ingredient.
Described high pressure hydrocarbon substance-containing slurry pump 8 is a kind of multicolumn plug surge pumps, for example the pump sold with Geho pump trade(brand)name with Feluwa pumpen trade(brand)name or Geho pump Holthuis B.V company of the intelligent merchant's engineering equipment in Shanghai company limited.
Fig. 4 is described three runner spraying guns, 30 telescoping structure synoptic diagram, and it has simple in structure, life cycle length, processing, assembling and advantage easy to maintenance.It directly influences the work-ing life of utilization ratio of raw materials, internal insulation material and spraying gun self, and simultaneously, its atomizing effect also will determine the quality of its synthetic gas.In addition, its major function is: one and interior heat preserving type air-flow bed coal-gasification reactor 11 form the flow field of coupling, the slagging scorification of heat preserving type air-flow bed coal-gasification reactor 11 in suppressing; It two fully atomizes hydrocarbon substance-containing slurry, promotes that hydrocarbon substance-containing slurry effectively mixes rapidly with vaporized chemical, the content of available gas composition in raising feed stock conversion and the synthetic gas.
Described three runner spraying guns 30 are made up of centre channel 63, interior ring passage 64 and outer ring channel 65, described centre channel 63 and outer ring channel 65 are vaporized chemical passages, ring passage 64 is hydrocarbon substance-containing slurry passages in described, utilize two strands of vaporized chemicals to make vaporized chemical form impact, mix to hydrocarbon substance-containing slurry with the contact position difference and the speed difference of hydrocarbon substance-containing slurry, and hydrocarbon substance-containing slurry fully atomizes under the effect of outlet atomizing angle, the efficiency of carbon conversion when improving the reaction of hydrocarbon substance-containing slurry generation incomplete combustion.In order effectively to protect three runner spraying guns 30; be provided with independently three runner spraying gun water coolant securing systems; except that being used to cool off the three runner spraying guns that are in the high-temperature zone, can also whether leakage situation take place according to the analyzing and testing three runner spraying gun water coolant securing systems of gas content in the outlet water coolant simultaneously.The structure of this securing system is the coil pipe cooled.
In Fig. 4, a 1, a 2Be three runner spraying gun cooling water intakeoutfall, by import a 1Feed water coolant, by outlet a 2Flow out, the effect of water coolant is three runner spraying guns under the protection hot conditions, avoids three runner spraying guns to be subjected to high temperature ablation; B is the hydrocarbon substance-containing slurry import, and the outside is connected with high pressure hydrocarbon substance-containing slurry pump 8 outlet conduits, and inner and interior ring passage 64 is connected, and this hydrocarbon substance-containing slurry is by the interior ring passage 64 in the three runner spraying guns; C is the import of the centre channel 63 of vaporized chemical, and its outside is connected with vaporized chemical pipeline 23, and centre channels 63 inner and in three runner spraying guns are connected, and this vaporized chemical is by centre channel 63; D is the import of the outer ring channel 65 of vaporized chemical, and its outside is connected with vaporized chemical pipeline 23, and outer ring channels 65 inner and in three runner spraying guns are connected, and this vaporized chemical is by outer ring channel 65; Centre channel 63 ends and interior ring passage 64 ends form 30～50 ° of angles, interior ring passage 64 ends and outer ring channel 65 ends form 50～90 ° of angles, and outer ring channel 65 forms 120～150 ° of angle (not shown in FIG.)s with the present invention's three runner spraying guns 30 ends.Centre channel 63, interior ring passage 64 are the gradual shrinkage structure with outer ring channel 65 in the end near three runner spraying guns.Centre channel 63 ends are interior ring passage 64 ends apart from 5～8 times of the distance of three runner spraying gun ends apart from the distance of three runner spraying gun ends.
By above structure, utilize vaporized chemical different with the flow velocity of slip, at first making the centre channel vaporized chemical that slip is formed to impact mixes, then under the shock action of outer ring channel 65 vaporized chemicals, slip is fully atomized, form the fine particle of decentralized, in interior heat preserving type air-flow bed coal-gasification reactor 11 reaction chambers, fully contact and carry out the incomplete combustion reaction and produce the high temperature crude synthesis gas with vaporized chemical.
Heat preserving type air-flow bed coal-gasification reactor 11 is cylindrical tube or the truncated cone barrel pressure containers that have lower cover in described, wherein these reactor 11 tops are reaction chamber, the bottom is a cooling room, three runner spraying guns, 30 installing ports 10 are arranged at the top, described three runner spraying guns 30 are fixed on the installing port 10, and material outlet is positioned at reaction chamber top; In these reactor 11 bottoms are cooling rooms, and this cooling room is provided with water coolant sparger 34, telescopic inner core 31 and urceolus 32, bubbling water-bath 33.
Fig. 5 is water coolant sparger 34 structural representations.The effect of this water coolant sparger 34 is to impel the water coolant that enters described reactor 11 to reach uniform distribution; evenly form the thick moisture film of 5～10mm at inner core 31 inwalls; guarantee that the high temperature crude synthesis gas that enters bubbling water-bath 33 along inner core 31 does not directly contact with inner core with high-temperature ash; effectively the protection inner core makes water coolant that high temperature crude synthesis gas and high-temperature ash are formed cooling simultaneously.
As shown in Figure 5; this sparger 34 is the shellring tubular structure; enter water coolant endless tube 66 outside the 180 ° of angles in both sides enter of water coolant sparger 34; being distributed with 8 uniform water pipes outside below the endless tube 66 links to each other with middle endless tube 67; being distributed with 16 uniform water pipes below the middle endless tube 67 links to each other with interior endless tube 68; the outside of interior endless tube has 36 uniform posticums; the water coolant that comes out from posticum flows to bottom bubbling water-bath 33 at the moisture film that the inwall of inner core evenly forms 5～10mm in the form of a ring, plays the effect of effective protection inner core and cooling down high-temperature crude synthesis gas and high-temperature ash.
This water coolant sparger 34 is connected with inner core 31 tops; Water coolant enters bubbling water-bath 33 in the cooling room bottom with high-temperature synthesis gas, high-temperature ash and stream by inner core 31 behind uniform distribution under 34 effects of described water coolant sparger, this bubbling water-bath 33 is combinations of a kind of upper cylinder, bottom cone, and water coolant, high-temperature synthesis gas, high-temperature ash are mixed in this bubbling water-bath 33 and high-temperature synthesis gas, high-temperature ash cooling are cooled off; Water coolant also protects inner core 31 not burnt out by high-temperature ash and high temperature crude synthesis gas simultaneously.The cylindrical shell height of heat preserving type air-flow bed coal-gasification reactor 11 cylindrical tubes or truncated cone cylindrical shell is 4 to 5 with the ratio of mean diameter in described.Preferably 4 to 4.8, more preferably be 4 to 4.5.
In interior heat preserving type air-flow bed coal-gasification reactor 11 reaction chambers, the different insulation of multilayer performance, heat insulation, high temperature material layer are set, wash away erosion material and make with standing high-temperature ash near the internal layer of reaction chamber, for example high-chrome brick; The middle layer is to have used heat-blocking action, prevents that the material of calorific loss from making, for example high alumina brick; Skin near reactor 11 housings is to have used insulation effect, and the material of reduction case temperature is made, for example the lightweight aluminium brick.
In interior heat preserving type air-flow bed coal-gasification reactor 11 reaction chambers, be provided with reactor 11 direct temperature measurement devices, utilize the pyrometer couple that inserts directly to measure the temperature of reaction chamber, the pyrometer couple top with concordant near the internal layer of reaction chamber or in the 10～20mm that contracts, temperature feedback situation by thermopair is regulated the gasification dosage and the hydrocarbon substance-containing slurry amount of heat preserving type air-flow bed coal-gasification reactor 11 in entering, and the temperature of heat preserving type air-flow bed coal-gasification reactor 11 reaction chambers is in above-mentioned temperature range in the control; Indirect temperature measuring equipment perhaps is set; use pyrometer couple to detect casing surface temperature; judge the operation conditions of this reactor 11; mainly refractory materials breaks down, three runner spraying guns break down or the high temperature crude synthesis gas occurs sees through the fault condition that refractory masses takes place by so-called " collaborating " in order to monitor, effectively the interior heat preserving type air-flow bed coal-gasification reactor 11 of protection.In order to support refractory materials, be provided with the refractory materials loading plate, bear whole loads of refractory materials own wt generation and the respective load that refractory liner generation longitudinal dilatation causes, the load that pressure reduction produces between heat preserving type air-flow bed coal-gasification reactor 11 reaction chambers and the cooling room in also bearing.
The high temperature crude synthesis gas that generates arrives syngas outlet pipeline 12 along the annular space between inner core 31 and the urceolus 32 through water quench, bubbling water-bath 33 coolings after removing lime-ash, under the principle that does not increase resistance drop, Liqiud-gas mixing device 62 can be set between the annular space of inner core 31 and urceolus 32, this device mixes moisture and the ash content in the synthetic gas, the crude synthesis gas of being convenient to leave annular space carries out gas-liquid separation, can avoid taking away a large amount of ashes and water from interior heat preserving type air-flow bed coal-gasification reactor 11 effusive synthetic gas.
According to the composition difference of requirement crude synthesis gas, described vaporized chemical can be selected pure oxygen, oxygen rich gas or air for use.Described vaporized chemical is selected from air.Described oxygen rich gas is that oxygen and one or more are selected from the mixture of the gas of nitrogen, argon gas, carbonic acid gas, wherein oxygen content is in this gaseous mixture cumulative volume 〉=90%, the preferably oxygen of purity 〉=99.5%, the more preferably oxygen of purity 〉=99.6%.Described vaporized chemical is pure oxygen or oxygen rich gas preferably, more preferably pure oxygen.
Described crude synthesis gas cooling dedusting, washing, purifying is from air-flow bed coal-gasification reactor 11 effusive crude synthesis gas, enter air water separator 13 by outlet conduit 12, in air water separator 13, be provided with gas-liquid separate component eddy flow plate 69, particularly, the structure of this air water separator 13 is to have upper cover, the cylindrical tube of lower cone, inside is provided with gas-liquid separate component eddy flow plate 69, it will wherein carry thin Ash Water Separator secretly by the collision of gas and eddy flow plate 69, isolatingly carry thin buck secretly and after decompression, deliver to and contain thin grey water treatment system, and crude synthesis gas enters gas-water mixer 15 through pipeline 14, and the structure of this gas-water mixer 15 is wikipedia type sleeves; According to gasification reaction and cooling situation, crude synthesis gas also can directly enter gas-water mixer 15 through pipeline 12 without air water separator 13.In gas-water mixer 15, crude synthesis gas with by 19 pressurizations of grey water-circulating pump after the buck thorough mixing that pipeline 20 is sent here, the thin ash of carrying secretly in the gas is soaked into fully by water and mixes after pipeline 16 enters gas wash tower 17.
Described gas wash tower 17 is a cylindrical pressure vessel, in gas wash tower 17, be provided with downtake 39, upcast 40, bubbling style water-bath storage tank 41, eddy flow plate 38, traverse baffle 37, tower tray 36 multistage washing devices, top is provided with scum dredger 35 simultaneously, they constitute in the following manner: downtake 39 tops link to each other with inlet pipe 16, upcast 40 is fixed on the tower body, all insert in the bubbling style water-bath storage tank 41 bottom, the top of bubbling style water-bath storage tank 41 sets gradually eddy flow plate 38, traverse baffle 37 and tower tray 36, and tower tray 36 tops are provided with scum dredger 35.Crude synthesis gas from gas-water mixer 15 arrives bottom bubbling style water-bath storage tank 41 by gas wash tower 17 downtakes 39, at first remove thin ash through 41 coolings of bubbling style water-bath storage tank, rise along the annular space between upcast 40 and the downtake 39 then, through eddy flow, baffling etc. collisions changes and flows to and by the downstream section phlegma or supply water in gas wash tower 17 outward through eddy flow plate 38, traverse baffle 37, multistage washing such as tower tray 36 back arrives top scum dredger 35, tower tray 36 can be a sieve-board type, bubble-cap formula or float-valve type tower tray, the synthetic gas of " totally " leaves gas wash tower 17 from the top along pipeline 26 after separating the liquid water of wherein carrying secretly under scum dredger 35 effects.Through after the multistage washing of gas wash tower 17, ash oontent can be reduced to 0.8mg/Nm in the exit gas 3Below, can be used as follow-up unstripped gas; Washing containing in the bubbling style water-bath storage tank 41 that thin buck collects in gas wash tower 17 bottoms behind the crude synthesis gas, on bubbling style water-bath storage tank 41 tops grey water out is set, the buck on these bubbling style water-bath storage tank 41 tops heat preserving type air-flow bed coal-gasification reactor 11 entrance of cooling water in a part is sent into along pipeline 21 after pipeline 18 is by grey water-circulating pump 19 pressure-raisings, making water coolant behind water coolant sparger 34 uniform distribution uses, a part is sent into gas-water mixer 15 and crude synthesis gas thorough mixing along pipeline 20 and is soaked into wherein thin ash, and these bubbling style water-bath storage tank 41 bottom ash contents are more contains thin buck and sent to by pipeline 27 after reducing pressure and contain thin grey water treatment system; Gas wash tower 17 used washing water have two strands, one comes the circulation buck after the self-contained thin grey water handing, enter bubbling style water-bath storage tank 41 from gas wash tower 17 middle and lower part imports, one replenishes from the downstream section phlegma or by outer water supply and enters between gas wash tower 17 middle and upper part tower trays 36 and the scum dredger 35.In order to keep the normal operation of gas wash tower 17, guarantee thorough washing, the purification of crude synthesis gas, contain the normal operation of thin grey water handing part, the unstripped gas of avoiding simultaneously discharging gas wash tower 17 has water, the thin grey discharge that contains that needs to control each strand washing flooding velocity and discharge gas wash towers 17 along pipeline 27, so that make the liquid level of bubbling style water-bath storage tank 41 normal, the turnover water yield is stable.
In addition, described cinder slag disposal facilities is set below interior heat preserving type air-flow bed coal-gasification reactor 11.Described cinder slag discharging is that the waste residue (being referred to as the cinder slag) of unconverted hydrocarbon substance and generation in the gasification reaction is discharged from interior heat preserving type air-flow bed coal-gasification reactor 11.Leave the cooling room that this reaction chamber enters reactor 11 in high-temperature synthesis gas and high-temperature ash that the reaction chamber of this reactor 11 generates, in this cooling room, water coolant is entering by inner core 31 in the bubbling water-bath 33 in the cooling room bottom with high-temperature synthesis gas, high-temperature ash and stream behind the uniform distribution under 34 effects of described water coolant sparger, described cinder slag is cooled after the water cooling, enters bottom cinder slag disposal facilities and drains.This cinder slag disposal facilities comprises lock slag valve 22, lock hopper 24 and vent valves 25.Described lock slag valve 22 and vent valves 25 are high temperature resistant, high pressure and wear resistance ball valve, for example U.S. Everlasting Valve Co company makes, the supply of U.S. tall and erect automatization Shanghai company limited with trade(brand)name ball catch slag valve product sold, Finland Neles-Jamesbury Oy company with trade(brand)name ball catch slag valve product sold, U.S. Metso Autommation Field Systems Division 44BowditchDrive company with trade(brand)name ball catch slag valve product sold.The non-type equipment that described lock hopper 24 is high temperature high voltage resistants is determined its size with the scale and the ash oontent in the slip of device.
Concrete cinder slag discharge process is as follows: when the cinder slag is collected, at first lock hopper 24 is carried out punching press, make the pressure of the pressure of lock hopper 24 and described reactor 11 basic identical, open lock slag valve 22 then, described cinder slag relies on the effect of self gravitation and circulating water flow to enter lock hopper 24 from bubbling water-bath 33, closes locking slag valve 22 after the cinder slag is collected and finished; When the cinder slag discharges, earlier lock hopper 24 is carried out release, unload to normal pressure and open cinder slag vent valves 25, the cinder slag relies on wash-down water pressure to discharge lock hopper 24, in order to impel the cinder slag to discharge smoothly and to prevent cinder slag vent valves 25 inner slag inclusions, lock hopper 24 is washed with wash-down water in tapping process, and wash-down water is from grey water pump 54 outlets, and flushing is closed cinder slag vent valves 25 after finishing.Whole cinder slag blowdown system is collected by the cinder slag and the discharging of cinder slag hockets finishes.
Also relate to the described thin grey water handing that contains in embodiments of the invention, describedly contain thin grey water handing and comprise that the thin buck that contains from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms flows out along pipeline 29, the thin buck that contains of gas wash tower 17 flows out and air water separator 13 is isolating contains thin buck and flow out along pipeline 28 along pipeline 27, they are through entering high-temperature water heater's 42 step-downs after the decompression respectively, the high temperature phlegma that returns from the back system also enters this high-temperature water heater 42, in this high-temperature water heater 42, can reclaim the heat of high temperature phlegma on the one hand, the loss that can replenish gasification system water on the other hand.Describedly contain that high temperature effusion gas that thin buck and high temperature phlegma overflow is most of to be steam after step-down, can adopt indirect heat exchange and direct heat exchange to reclaim heat; Described high-temperature water heater 42 is high temperature resistant bearing devices, column plate is set in order to gas-water separation on top, determines its size according to the calculating of how much passing through that enters the water yield.The major advantage of described indirect heat exchange is that the non-condensable gas that step-down is overflowed can not come back to gas wash tower 17, overflows thoroughly; When vapor pressure is higher, because noncondensable gas solubleness in the circulation buck is big, the general method of grey water-to-water heat exchanger 57 indirect heat exchanges that adopts reclaims heat, needs simultaneously to add dispersion agent at degassing tank 55 water outlets or in degassing tank 55, avoids the fouling of pipeline and interchanger.Described degassing tank 55 is the jar structures high temperature resistant for sleeping in that have dome head, determines its size according to the composition of trace element in the size of the water yield and the water.
On meaning of the present invention, the major advantage of direct heat exchange is that heat exchange is more thorough, the heat utilization ratio height; When vapor pressure was relatively lower, because the corresponding reduction of circulating ash water pressure, the solubleness of noncondensable gas in the circulation buck was less, and it is little that noncondensable gas is got back to gas wash tower 17 back influences on a small quantity, can adopt direct heat exchange recovery heat in reclaiming hot-water tower 60.
When indirect heat exchange, describedly contain thin buck and high temperature phlegma effusion gas after the high temperature step-down enters grey water-to-water heat exchanger 57, the circulation buck heat temperature raising of in grey water-to-water heat exchanger 57, degassing water pump 56 being sent here, the circulation buck after the intensification arrives bottom bubbling style water-bath storage tank 41 by gas wash tower 17 middle and lower part imports; Step-down effusion gas by grey water-to-water heat exchanger 57 heat exchange after, major part is condensed into liquid and enters air water separator 45, gas is gone out burning emptying or be sent to follow-up workshop section and reclaim from air water separator 45 tops, separate water outlet and come back to degassing tank 55.Described grey water-to-water heat exchanger 57 is floating head type tubular structures known to those skilled in the art, and the size of its heat interchanging area and material need to determine according to characteristic, temperature, the amount of medium.Described air water separator 45 is the cylindrical overpressure resistant barrels that have end socket up and down, and it is provided with eddy flow plate 70 for void tower or on top.
During direct heat exchange, described thin buck and the high temperature phlegma effusion gas after the high temperature step-down of containing enters and reclaims hot-water tower 60, in reclaiming hot-water tower 60 to from the buck direct heating of degassing tank 55 through water pump 56 pressure-raisings that outgas, effusion non-condensable gas small part after the cooling is dissolved in the circulation buck, most of go out burning or be sent to subsequent processing and reclaim from the top of reclaiming hot-water tower 60, described recovery hot-water tower 60 is the cylindrical overpressure resistant barrels that have end socket up and down, and inside has normally used cone separator in this technical field; Behind pressure-raising pump 61 pressure-raisings, arrived bottom bubbling style water-bath storage tanks 41 by high temperature step-down effusion gas heating and the circulation buck that is dissolved with a part of noncondensable gas by gas wash tower 17 middle and lower part imports.Containing thin buck through concentrated after high-temperature water heater's 42 step-downs enters low-temperature water heating device 43 and carries out the low temperature step-down after decompression once more, the evolving gas of the low temperature step-down overwhelming majority enters degassing tank 55 for steam in low-temperature water heating device 43, wherein said low-temperature water heating device 43 is heatproof bearing devices, and top is provided with column plate in order to gas-water separation.This low temperature step-down evolving gas can or directly enter the thermal source of degassing tank 55 as grey water degasification, perhaps behind condenser 59, enter the thermal source of de aerated water groove 55, the quantity of steam of condenser 59 outlets is carried out regulating and controlling by the cooling water inflow size as grey water degasification.After step-down once more, concentrate and contain thin buck and enter vacuum evaporator 44 and carry out step-down in low-temperature water heating device 43 bottoms, vacuum evaporator 44 also receives the pulp water of thick slag discharge unit simultaneously, escaping gas enters negative pressure separator 46 after the 58 cooling coolings of negative pressure condenser in vacuum evaporator 44, gas enters off-gas pump 47 imports after separating moisture wherein, the gas that comes out from off-gas pump 47 separates gas emptying behind the moisture in off-gas pump separator 48, off-gas pump separator 48 isolated water and negative pressure separator 46 bottom water all flow into aqua storage tank 52.Described vacuum evaporator 44 is that heatproof is born negative pressure equipment, column plate is set in order to gas-water separation on top.Described negative pressure separator 46 is the low temperature resistant equipment that bears negative pressure, and it is provided with eddy flow plate 71 in order to gas-water separation for void tower or on top.The normal temperature equipment that described off-gas pump separator 48 is anti-low pressure, it is provided with eddy flow plate 72 in order to gas-water separation for void tower or on top.Vacuum evaporator 44 bottoms concentrate and to contain thin buck enter natural subsidence ash disposal in the clarifying tank 50 behind clarifying tank feeding pump 49 pressure-raisings.To wash the thin grey suspended substance flocculation in the buck and accelerate settling velocity in order to impel to concentrate to contain, need in clarifying tank, add flocculation agent usually.
On meaning of the present invention, described flocculation agent should be appreciated that it is the agent that impels thin grey rapid subsidence, it is a kind of agent that is selected from polymerization ferrous sulfate, polymerize aluminum chloride and molecular weight at 1200～1,500 ten thousand polyacrylamide, for example Nanjing open the light company with trade(brand)name BC-644 product sold, Tianjin Chemical Research ﹠ Desing Inst with trade(brand)name polymer flocculating agent product sold.Those skilled in the art can be according to containing the thin grey water yield by the definite amount that adds flocculation agent of test, and thin ash is deposited in clarifying tank 50 bottoms behind the adding flocculation agent, and the top water overflow enters aqua storage tank 52.Flow into the buck from negative pressure separator 46 of aqua storage tank 52, from the buck of off-gas pump separator 48, enter degassing tank 55 from clarifying tank 50 top overflowing ash waters part behind grey water pump 54 pressure-raisings, a part is as wash-down water, small part effluxes carries out water treatment, the main purpose that effluxes is in order to keep the balance of solubility salt in the buck, to alleviate equipment and Corrosion of Pipeline.
Can discharge the mouth of a river or in degassing tank 55, add dispersion agent at degassing tank 55, in order to reduce the fouling degree of heat-exchange equipment and ash-water pipeline.Described dispersion agent should be appreciated that it is the agent that dissolved gases overflows, delays fouling fast in the promotion water; Described dispersion agent is one or more vinylformic acid-alkyl acrylate fat that are selected from the acrylic acid or the like copolymer, 30～60% (weight) of 4～10% (weight) hydrolysis maleic anhydride, 30～60% (weight)-the contain agent of the unsaturated monomer class terpolymer of sulfonic acid group, preferably agent of the acrylic acid or the like copolymer of 4～10% (weight) hydrolysis maleic anhydride, 30～60% (weight); Be more preferably the agent of 4～10% (weight) hydrolysis maleic anhydride.For example Tianjin Chemical Research ﹠ Desing Inst with trade(brand)name high temperature dirt dispersion agent product sold, the calm and peaceful water treatment in Shandong company with trade(brand)name TH-504 product sold.Described dispersant dosage is that preferably 60～75PPm is more preferably 65～70PPm in pending thin grey water yield gross weight 50～80PPm.The buck that removes after thin ash also outgases carries out pressure-raising by degassing water pump 56, insufficient section enters degassing tank 55 by make up water, buck behind the pressure-raising, perhaps enter grey water-to-water heat exchanger 57, carry out indirect heat exchange with high temperature step-down effusion gas, the circulation buck after the intensification arrives gas wash tower 17 bottom bubbling style water-bath storage tanks 41 by gas wash tower 17 middle and lower part imports and recycles; Perhaps enter and reclaim hot-water tower 60 and the direct heat exchange of high temperature step-down effusion gas, the circulation buck after the intensification is sent into gas wash tower 17 middle and lower part imports through pressure-raising pump 61, arrives gas wash tower 17 bottom bubbling style water-bath storage tanks 41 and recycles.
Clarifying tank 50 bottom ash contents enter vacuum band-type filter machine 51 after thin buck passes through filter feeding pump 53 pressure-raisings higher concentrated containing, in vacuum band-type filter machine 51 with thin lime-ash and water sepn, thin lime-ash is collected the back and is discharged, and isolated water comes back in the clarifying tank 50.Described vacuum band-type filter machine 51 be for example Nuclear Industry Yantai Tongxing Industry Co., Ltd with trade(brand)name vacuum band-type filter machine product sold, Huzhou examine the mechanical company limited of rich filtration with trade(brand)name vacuum band-type filter machine product sold, Tianhe Machinery Equipment Co., Ltd., Shijiazhuang with trade(brand)name vacuum band-type filter machine product sold.
The invention still further relates to the product that adopts the inventive method to produce, that for example adopts that the inventive method produces contains CO, H 2And CO 2Be the synthetic gas of main ingredient, its CO content can reach more than 45% (the butt volume), H 2Content can reach more than 33% (the butt volume), CO 2Content can reach below 20% (the butt volume).
CO, H in the product of the present invention 2And CO 2Analytical procedure adopt GB/T17132-1997.
The invention still further relates to and adopt the inventive method to produce the purposes of product, for example the H2 of reaction generation purifies by additive method and can be used as the unstripped gas of the required unstripped gas of gelatin liquefaction, Hydrogen Energy battery, the reducing gas of metallurgical project; Contain CO, H 2And CO 2For the synthetic gas of main ingredient can be used for synthesizing methanol, ammonia, dme, alkene, producing acetic acid by carbonylation method, aceticanhydride etc., also can be used to generate electricity, the unstripped gas of heat, chemical etc., also can be used for IGCC combined cycle generation project supply raw materials gas and fuel gas simultaneously.
[beneficial effect]
The present invention has following positively effect.
1, since the inventive method adopted and prior art diverse in heat preserving type air-flow bed coal-gasification reactor 11, so method of the present invention has been expanded raw material subject range greatly, for example, method of the present invention can be used and variously contain hydrocarbon solid-state or fluent meterial as raw material, and prior art is just made raw material with fine bituminous coal.
2, the vaporized chemical choice is bigger, and according to the requirement difference of follow-up workshop section to the unstripped gas composition, vaporized chemical of the present invention can be selected pure oxygen, oxygen rich gas or air.
3, because the present invention has adopted and diverse crude synthesis gas washing of prior art and purification techniques, so adopt the thin ash content of the inventive method production synthetic gas to be lower than 0.8mg/Nm 3, and prior art generally reaches 2mg/Nm 3, therefore, it is obviously on the low side that the present invention produces the thin ash content of synthetic gas.
4, because grinding body gradation is reasonable and additive is used, and it is higher to produce hydrocarbon substance-containing slurry concentration, and is easy to pumping, so the energy consumption of the inventive method is lower, compared with prior art, energy consumption reduces more than 10%.In addition, because hydrocarbon substance-containing slurry concentration height, reaction consumption gasification dosage is less, and heat energy utilization is reasonable, and cold gas efficiency height ratio prior art exceeds more than 2%.
5, the present invention has adopted and has contained thin buck recycle utilization after treatment, make whole hydrocarbon substance-containing slurry pressurized high-temperature gasification system waste water, discharge amount of exhaust gas little, compared with prior art, waste water, discharge amount of exhaust gas reduce more than 30%, therefore, method of the present invention is environmentally friendly.
In a word, method of the present invention is utilized industrial or agricultural and people's sanitary waste, turn waste into wealth, at lower cost with environmental friendliness produce the energy and Industrial products with high value, realize the benign cycle of recycling economy, for China's emission reduction tasks is made significant contribution.
[description of drawings]
Fig. 1 is that the gasification of hydrocarbon substance-containing slurry pressurized high-temperature cools except that the lime-ash schema with crude synthesis gas;
Fig. 2 is that indirect heat exchange contains thin grey water handing schema;
Fig. 3 is that direct heat exchange contains thin grey water handing schema;
Fig. 4 is three runner atomizer structure synoptic diagram;
Fig. 5 is a water coolant structure of distributor synoptic diagram.
[embodiment]
Embodiment 1: use great river, Guizhou coal to implement method of the present invention as raw material.Described raw material thermal value: 26600J/g, the principal element analytical results is as follows:
Ultimate analysis Carbon Cd hydrogen Hd nitrogen Nd sulphur Sd oxygen Od % (weight) % (weight) % (weight) % (weight) % (weight) 64.77 4.35 1.10 1.50 6.28
The operational condition that adopts is as follows: after great river, Guizhou coal is removed the iron that wherein may exist with magnet, re-using Shanghai magnificent machinofacture far away company limited produces impact breaker and is crushed to granularity less than 30mm, allow this coal dust and water then, additive, auxiliary agent, the rod mill of sending into the production of Jiangsu Jiangyin Yate Machinery Manufacturing Co., Ltd. carries out a wet method and grinds altogether, the described slip of making hydrocarbon substance-containing slurry concentration 65.0% (weight), water-content 35% (weight) wherein, dry coal content 64.64% (weight), sodium lignosulfonate additive level 0.32% (weight), caustic soda content 0.04% (weight), slip total flux 48452.6kg/h; Slip at first flows automatically and enters slip medial launder 3, send into slip storage tank 6 by low pressure shurry pump 4, stir after high pressure hydrocarbon substance-containing slurry pump 8 pressure-raisings behind 7.8Mpa, are sent into ring passages 64 in the interior heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying guns 30 at agitator; Vaporized chemical is the pure oxygen of concentration 99.6% (volume), with oxygen pressure mention deliver to behind the 8.2Mpa in the outer ring channel 65 and the centre channel 63 of heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying guns 30, the oxygen total flux is 20101.5Nm 3/ h, above-mentioned pure oxygen atomizes above-mentioned slip fully in three runner spraying gun exits, the reaction chamber of heat preserving type air-flow bed coal-gasification reactor 11 in delivering to then, in reaction chamber, under 1390 ℃ of working pressure 6.5MPa and temperature of reaction, carry out violent incomplete combustion reaction, the high temperature crude synthesis gas that generates, high-temperature ash, the water coolant of unconverted carbon and the flow 177560kg/h that enters water coolant sparger 34 is by inner core 31 and flow into bottom bubbling water-bath 33, heat preserving type air-flow bed coal-gasification reactor 11 in after ash is washed in bubbling water-bath 33 cooling, leaving along the annular space between inner core 31 and the urceolus 32,251 ℃ of its temperature, pressure 6.47MPa, gaseous constituent and flow thereof are analyzed according to GB/T17132-1997, thin ash content is analyzed according to GB/T1574-1995, these analytical resultss are listed in the table below 1, ash content in unconverted carbon and the raw material is discharged by lock hopper 24 with thick slag form, this thick slag temperature is 76 ℃, and flow is in butt 4545.8kg/h.
Table 1
Figure C20081013297500251
Is that the buck of 85561kg/h enters gas-water mixer 15 from the crude synthesis gas of interior heat preserving type air-flow bed coal-gasification reactor 11 with the flow behind grey water-circulating pump 19 pressure-raisings of passing through from gas wash tower 17, mix through gas-water mixer 15, by sending into follow-up system as unstripped gas by pipeline 26 after gas wash tower 17 ash disposal, ash content in the unstripped gas of washing back is analyzed according to GB/T1574-1995, its ash content is reduced to less than 0.8mg/Nm3,242 ℃ of temperature, pressure 6.27MPa, gaseous constituent and flow are analyzed according to GB/T17132-1997, and its analytical results is listed in table 2:
Table 2
Sequence number The component molecular weight Nm3/h Vol% wet basis volume Vol% butt volume
1 H22 20586.18 14.50 35.07
2 CO28 26513.82 18.68 45.16
3 CO244 10852.57 7.64 18.49
4 H2S34 305.07 0.21 0.52
5 COS60 33.07 0.02 0.06
6 CH416 54.34 0.04 0.09
7 N228 280.51 0.20 0.48
8 Ar39.9 80.38 0.06 0.14
9 H2O18 83260.21 58.65
10 Gas amounts to Nm3/h 141966.15 100.00 100
The thin buck that contains from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms discharge, after step-down, send in the high-temperature water heater 42 who contains thin grey water handing part from the thin buck that contains that gas wash tower 17 is discharged, meanwhile the phlegma of lower procedure is also delivered among the high-temperature water heater 42, wherein the temperature that contains thin buck of discharging from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms is 252 ℃, flow 86532kg/h, thin ash content 1.83% (weight); The temperature that contains thin buck that gas wash tower 17 is discharged is 244 ℃, flow 19403kg/h, thin ash content 1.79% (weight); The temperature of this phlegma is 95 ℃, flow 7000kg/h.Described thin buck and the described phlegma of containing carries out the step-down cooling by high-temperature water heater 42, is 0.86MPa with pressure-controlling, is dissolved in gas in the water and overflows and enter grey water-to-water heat exchanger 57, evolving gas total flux 18636Nm 3/ h, steam content 99.2% (volume) wherein, 179 ℃ of temperature, the circulation buck heat temperature raising of in grey water-to-water heat exchanger 57, degassing water pump 56 being sent here, its circulating ash discharge is 114404kg/h, 109 ℃ of temperature, the circulation buck after the intensification are passed through gas wash tower 17 middle and lower part imports with 162.5 ℃ of grey discharge 114404kg/h temperature and are arrived bottom bubbling style water-bath storage tanks 41; The air-water mixture of ash discharge water heater 57 is 170Nm with the gas flow 3/ h, liquid water flow 14838kg/h delivers to air water separator 45, discharge from the top by air water separator 45 back gases, and isolating buck returns degassing tank 55 for 105 ℃ with flow 14838kg/h, temperature; In addition, contain thin buck and deliver to low-temperature water heating device 43 with flow 98048kg/h, thin ash content 2.0% (weight) by 42 of high-temperature water heaters are spissated, with pressure-controlling at 0.15MPa, after decrease temperature and pressure by top effusion gas with flow 11686Nm 3/ h, temperature are delivered to degassing tank 55 for 128 ℃, and the bottom concentrated solution is delivered in the vacuum evaporator 44 with flow 88658kg/h, thin ash content 2.2% (weight), meanwhile the pulp water of cinder slag discharge unit is delivered to vacuum evaporator 44 with flow 41061kg/h, thin ash content 1.2% (weight), vacuum evaporator is controlled at 68.7 ℃ of pressure-0.03MPa, temperature, by vacuum evaporator 44 top escaping gas with flow 10568Nm 3/ h, behind negative pressure condenser 58, deliver to negative pressure separator 46, gas is delivered to off-gas pump 47 after separating moisture, negative pressure separator 46 parting liquids enter aqua storage tank 52 with flow 8492kg/h, and vacuum evaporator 44 bottom concentrated solutions are delivered to clarifying tank 50 with flow 121226kg/h, thin ash content 2.0% (weight) by clarifying tank feeding pump 49.Thin ash in the described concentrated solution is carrying out natural subsidence in described concentrated solution weight 0.001%, molecular weight under the effect of 1200～1,500 ten thousand polyacrylamide flocculants, then by sending into vacuum band-type filter machine 51 after 53 pressurizations of filter feeding pump, filtration obtains the thin ash of concentration 49.3% (weight), flow 4917kg/h, and its filtrate turns back to clarifying tank 50 with flow 18750kg/h.Clarifying tank 50 overflow waters are delivered to aqua storage tank 52 with flow 116310kg/h, and off-gas pump separator 48 isolating bucks flow to this aqua storage tank 52 with buck total flux 8700kg/h simultaneously.All water small portions behind grey water pump 54 pressure-raisings that flow into aqua storage tank 52 efflux processing with flow 12203kg/h, a part is delivered to degassing tank 55 with flow 70130kg/h, a part is returned as wash-down water with flow 51169kg/h, degassing tank 55 also needs to replenish a part of water with total flux 25102kg/h simultaneously, phlegma and Yuan Shui comprising follow-up system, in degassing tank 55, add Tianjin Chemical Research ﹠ Desing Inst with trade(brand)name high temperature dirt dispersion agent product sold dispersion agent, add-on is in buck weight 65ppm in the degassing tank 55, allow in the water after the emptying of dissolved noncondensable gas, buck is with flow 114404kg/h, temperature is delivered to grey water grey water interchanger 57 for 109 ℃ behind degassing water pump 56 pressure-raisings, be elevated to 162.5 ℃ from high-temperature water heater's 42 top step-down effusion vapour temperature after heating, delivered to bubbling style water-bath storage tank 41 by gas wash tower 17 middle and lower part imports again.
Embodiment 2: use the Firing Shenhua Coal liquefied residue to implement method of the present invention as main raw material.Raw material thermal value: 31580J/g, ultimate analysis is as follows:
Ultimate analysis Carbon Cad hydrogen Had nitrogen Nad sulphur St.ad oxygen Oad fluorine ad chlorine Clad % (weight) % (weight) % (weight) % (weight) % (weight) μ g/g % (weight) 75.78 4.58 0.83 2.34 1.08 70 0.014
The embodiment of this embodiment is identical with embodiment 1, only be to use Firing Shenhua Coal liquefied residue, water, calcium lignin sulphonate, caustic soda, the ratio of described Firing Shenhua Coal liquefied residue, water, calcium lignin sulphonate, caustic soda is respectively in its material gross weight 75.5%, 24.0%, 0.3%, 0.2%, make the slip that contains hydrocarbon material concentration 76% (weight), its flow control is 50kg/h; Send into ring passages 64 in the interior heat preserving type air-flow bed coal-gasification reactor 11 inner three runner spraying guns 30 by high pressure hydrocarbon substance-containing slurry pump pressure-raising to 7.8MPa, vaporized chemical adopts concentration 99.6% (volume) pure oxygen, oxygen flow 26.85Nm 3/ h, heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying gun centre channel 63 and outer ring channels 65 under 8.5MPa pressure, sending into, interior heat preserving type air-flow bed coal-gasification reactor 11 working pressure 6.5MPa, 1350 ℃ of temperature of reaction, the incomplete combustion reaction takes place under High Temperature High Pressure, lower the temperature except that heat preserving type air-flow bed coal-gasification reactor 11 in leaving behind the thick slag, the flow 75.3Nm of resultant dried synthetic gas by interior heat preserving type air-flow bed coal-gasification reactor 11 bottom cooling rooms 3/ h, 251 ℃ of temperature, CO+H 2Content 86.8% (butt volume), butt cinder quantity of slag 7kg/h is from gas wash tower 17 effusive dried synthetic gas flow 75.2Nm3/h, 241 ℃ of temperature, CO+H 2Content 86.9% (butt volume).
Effusive to go to contain the discharge of washing grey water handing be 140Kg/h from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms, thin ash content 1.6% (weight); Remove the pulp water flow 60Kg/h of vacuum evaporator 44, thin ash content 1.2% (weight); Effusive to go to contain the discharge of washing grey water handing be 40Kg/h from gas wash tower 17, thin ash content 1.6% (weight).
Through containing wash the grey water handing decrease temperature and pressure after, the grey discharge of returning gas wash tower 17 is 150Kg/h, 163 ℃ of temperature, outer drain discharge 35Kg/h, the thin ash concentration that obtains after filtering through vacuum band-type filter machine is 50%, flow is 7.2Kg/h.
Embodiment 3: account for 2/3 with shenfu coal weight and account for 1/3 mixture with refinery coke weight and implement method of the present invention as main raw material.The thermal value of this raw material: 28976J/g, ultimate analysis is as follows:
Ultimate analysis Carbon Cad hydrogen Had nitrogen Nad sulphur St.ad oxygen Oad fluorine ad chlorine Clad % (weight) % (weight) % (weight) % (weight) % (weight) μ g/g % (weight) 70.02 4.07 0.91 0.4 9.2 68 0.015
The embodiment of this embodiment is identical with embodiment 1 process, and just interior insulation is the pressure difference of air-flow bed coal-gasification reactor 11, the raw material difference of use.Use with shenfu coal weight account for 2/3 with refinery coke weight account for 1/3 mixture, water, sodium lignosulfonate, caustic soda, the ratio of described coal tar mixture, water, sodium lignosulfonate, caustic soda is respectively in its material gross weight 62.55%, 37%, 0.35%, 0.1%, flow 19856.6kg/h, ring passage 64 in the heat preserving type air-flow bed coal-gasification reactor 11 inner three runner spraying guns 30 in high pressure hydrocarbon substance-containing slurry pump pressure-raising is sent into to the 5.2MPa; Vaporized chemical adopts concentration 99.6% (volume) pure oxygen, oxygen flow 8309Nm 3/ h, heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying gun centre channel 63 and outer ring channels 65 under 5.5MPa pressure, sending into, interior heat preserving type air-flow bed coal-gasification reactor 11 working pressure 4.0MPa, 1320 ℃ of temperature of reaction, the incomplete combustion reaction takes place under High Temperature High Pressure, except that heat preserving type air-flow bed coal-gasification reactor 11 in leaving behind the thick slag, obtain dried synthetic gas flow 25204Nm by interior heat preserving type air-flow bed coal-gasification reactor 11 bottom cooling room coolings 3/ h, 222 ℃ of temperature, CO+H 2Content 81.6% (butt volume), butt cinder quantity of slag 1443kg/h is from gas wash tower 17 effusive synthetic gas flow 25200Nm3/h, 213 ℃ of temperature, CO+H 2Content 81.6% (butt volume).
Effusive to go to contain the discharge of washing grey water handing be 29500Kg/h from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms, thin ash content 1.75% (weight); Remove the pulp water flow 18010Kg/h of vacuum evaporator 44, thin ash content 1.1% (weight); Effusive to go to contain the discharge of washing grey water handing be 7100Kg/h from gas wash tower 17, thin ash content 1.72% (weight).
Through containing wash the grey water handing decrease temperature and pressure after, the grey discharge of returning gas wash tower 17 is 40600Kg/h, 155 ℃ of temperature, outer drain discharge 8500Kg/h, the thin ash concentration that obtains after filtering through vacuum band-type filter machine 51 is 45%, flow is 1859Kg/h.
Embodiment 4: implement method of the present invention with the Gansu coal liquefaction residue as main raw material.Raw material thermal value: 22410J/g, ultimate analysis is as follows:
Ultimate analysis Carbon Cad hydrogen Had nitrogen Nad sulphur St.ad oxygen Oad fluorine ad chlorine Clad % (weight) % (weight) % (weight) % (weight) % (weight) μ g/g % (weight) 52.17 3.86 1.22 2.74 1.25 254 0.017
The embodiment of this embodiment is identical with embodiment 1, only be to use Gansu coal liquefaction residue, water, polycondensation sodium naphthalene sulfonate, caustic soda, the ratio of described Gansu coal liquefaction residue, water, polycondensation sodium naphthalene sulfonate, caustic soda is respectively in its material gross weight 77.5%, 22%, 0.3%, 0.2%, flow 50kg/h, ring passage 64 in the heat preserving type air-flow bed coal-gasification reactor 11 inner three runner spraying guns 30 in high pressure hydrocarbon substance-containing slurry pump pressure-raising is sent into to the 7.8MPa; Vaporized chemical adopts concentration 99.6% (volume) pure oxygen, oxygen flow 19.1Nm 3/ h, heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying gun centre channel 63 and outer ring channels 65 under 8.2MPa pressure, sending into, the working pressure 6.5MPa of interior heat preserving type air-flow bed coal-gasification reactor 11,1300 ℃ of temperature of reaction, the incomplete combustion reaction takes place under High Temperature High Pressure, except that heat preserving type air-flow bed coal-gasification reactor 11 in leaving behind the thick slag, obtain dried synthetic gas flow 58Nm by interior heat preserving type air-flow bed coal-gasification reactor 11 bottom cooling room coolings 3/ h, 251 ℃ of temperature, CO+H 2Content 85.4% (butt volume), cinder quantity of slag 15.1kg/h butt is from gas wash tower 17 effusive dried synthetic gas flow 58Nm3/h, 242 ℃ of temperature, CO+H 2Content 85.5% (butt volume).
Effusive to go to contain the discharge of washing grey water handing be 240Kg/h from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms, thin ash content 1.95% (weight); Remove the pulp water flow 120Kg/h of vacuum evaporator 44, thin ash content 1.6% (weight); Effusive to go to contain the discharge of washing grey water handing be 80Kg/h from gas wash tower 17, thin ash content 1.92% (weight).
Through containing wash the grey water handing decrease temperature and pressure after, the grey discharge of returning gas wash tower 17 is 260Kg/h, 162 ℃ of temperature, outer drain discharge 45Kg/h, the thin ash concentration that obtains after filtering through vacuum band-type filter machine 51 is 50%, flow is 16.2Kg/h.
Embodiment 5: account for 2/3 with Firing Shenhua Coal liquefied residue weight and account for 1/3 mixture with shenfu coal weight and implement method of the present invention as main raw material.Raw material thermal value: 30076J/g, ultimate analysis is as follows:
Ultimate analysis Carbon Cad hydrogen Had nitrogen Nad sulphur St.ad oxygen Oad fluorine ad chlorine Clad % (weight) % (weight) % (weight) % (weight) % (weight) μ g/g % (weight) 73.91 4.33 0.78 1.82 4.08 68 0.015
The embodiment of this embodiment is identical with embodiment 1, only be to use with Firing Shenhua Coal liquefied residue weight account for 2/3 with shenfu coal weight account for 1/3 mixture, water, high polymerization sodium naphthalene sulfonate, sodium hydroxide, the ratio of described liquefied residue coal mixtures, water, high polymerization sodium naphthalene sulfonate, sodium hydroxide is respectively in its material gross weight 71.45%, 28%, 0.35%, 0.2%, flow 50kg/h, ring passage 64 in the heat preserving type air-flow bed coal-gasification reactor 11 inner three runner spraying guns 30 in high pressure hydrocarbon substance-containing slurry pump pressure-raising is sent into to the 7.8MPa; Vaporized chemical adopts concentration 99.6% (volume) pure oxygen, oxygen flow 23.7Nm3/h, heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying gun centre channel 63 and outer ring channels 65 under 8.2MPa pressure, sending into, the working pressure 6.5MPa of interior heat preserving type air-flow bed coal-gasification reactor 11,1350 ℃ of temperature of reaction, the incomplete combustion reaction takes place under High Temperature High Pressure, lower the temperature except that heat preserving type air-flow bed coal-gasification reactor 11 in leaving behind the thick slag by interior heat preserving type air-flow bed coal-gasification reactor 11 bottom cooling rooms, obtain dried synthetic gas flow 69.2Nm3/h, 251 ℃ of temperature, CO+H 2Content 85.6% (butt volume), cinder quantity of slag 6.4kg/h butt is from gas wash tower 17 effusive dried synthetic gas flow 69.1Nm3/h, 242 ℃ of temperature, CO+H 2Content 85.6% (butt volume).
Effusive to go to contain the discharge of washing grey water handing be 120Kg/h from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms, thin ash content 1.83% (weight); Remove the pulp water flow 40Kg/h of vacuum evaporator 44, thin ash content 1.5% (weight); Effusive to go to contain the discharge of washing grey water handing be 30Kg/h from gas wash tower 17, thin ash content 1.8% (weight).
Through containing wash the grey water handing decrease temperature and pressure after, the grey discharge of returning gas wash tower 17 is 130Kg/h, 163 ℃ of temperature, outer drain discharge 35Kg/h, the thin ash concentration that obtains after filtering through vacuum band-type filter machine 51 is 50%, flow is 6.6Kg/h.
Embodiment 6: implement method of the present invention with the Henan Yima coal as main raw material.Raw material thermal value: 25240J/g, principal element is analyzed as follows:
Ultimate analysis Carbon Cd hydrogen Hd nitrogen Nd sulphur Sd oxygen Od % (weight) % (weight) % (weight) % (weight) % (weight) 63.63 4.19 0.76 0.80 12.95
The embodiment of this embodiment is identical with embodiment 1, only be to use Henan Yima coal, water, high polymerization sodium naphthalene sulfonate, yellow soda ash, the ratio of described coal, water, high polymerization sodium naphthalene sulfonate, yellow soda ash is respectively in its material gross weight 61.5%, 38%, 0.3%, 0.2%, flow 68613.5kg/h, ring passage 64 in the heat preserving type air-flow bed coal-gasification reactor 11 inner three runner spraying guns in high pressure hydrocarbon substance-containing slurry pump pressure-raising is sent into to the 7.8MPa; Vaporized chemical adopts concentration 99.6% (volume) pure oxygen, oxygen flow 25104.8Nm 3/ h, heat preserving type air-flow bed coal-gasification reactor 11 3 runner spraying gun centre channel 63 and outer ring channels 65 under 8.5MPa pressure, sending into, the working pressure 6.5MPa of interior heat preserving type air-flow bed coal-gasification reactor 11,1390 ℃ of temperature of reaction, the incomplete combustion reaction takes place under High Temperature High Pressure, lower the temperature except that heat preserving type air-flow bed coal-gasification reactor 11 in leaving behind the thick slag, dried synthetic gas flow 74319.8Nm by interior heat preserving type air-flow bed coal-gasification reactor 11 bottom cooling rooms 3/ h, 252 ℃ of temperature, CO+H 2Content 78.8% (butt volume), cinder quantity of slag 5482.5kg/h butt is from gas wash tower 17 effusive dried synthetic gas flow 74212.6Nm3/h, 242.2 ℃ of temperature, CO+H 2Content 78.8% (butt volume).
Effusive to go to contain the discharge of washing grey water handing be 111800Kg/h from interior heat preserving type air-flow bed coal-gasification reactor 11 cooling rooms, thin ash content 1.12% (weight); Remove the pulp water flow 48100Kg/h of vacuum evaporator 44, thin ash content 2.76% (weight); Effusive to go to contain the discharge of washing grey water handing be 18760Kg/h from gas wash tower 17, thin ash content 2.4% (weight).
Through containing wash the grey water handing decrease temperature and pressure after, the grey discharge of returning gas wash tower 17 is 137513Kg/h, 163 ℃ of temperature, outer drain discharge 18118Kg/h, the thin ash concentration that obtains after process vacuum band-type filter machine 51 filters is 48%, and flow is 6312.5Kg/h.

Claims (8)

1, a kind of method of using producing synthesis gas from hydrocarbon substance-containing slurry is characterized in that this method comprises the steps:
The preparation of A, hydrocarbon substance-containing slurry: one or more solid-state and/or liquid hydrocarbon material, water, auxiliary agent and additive aqueous mixtures of containing are ground in grinding machine (1), prepare the slip that contains hydrocarbon material; Described auxiliary agent is that one or more are selected from CaCO 3Content 〉=the Wingdale of 95 weight %, FeSO 4, K 2CO 3, Na 2CO 3, ammoniacal liquor or caustic soda auxiliary agent, described additive is one or more additives that are selected from sodium lignosulfonate, calcium lignin sulphonate, polycondensation sodium naphthalene sulfonate, high polymerization sodium naphthalene sulfonate or non-gelationus high phosphorus china clay;
The pressurized high-temperature gasification of B, hydrocarbon substance-containing slurry: the hydrocarbon substance-containing slurry that allows above-mentioned steps A obtain enters in the reaction chamber of this reactor (11) by three runner spraying guns (30) in interior heat preserving type air-flow bed coal-gasification reactor (11), under the condition of 1250 ℃-1500 ℃ of temperature and pressure 0.1～10MPa, carry out violent incomplete combustion reaction, generate and contain CO, H with vaporized chemical from pipeline (23) 2And CO 2The high temperature crude synthesis gas of main ingredient and the mixture of high-temperature ash; Described vaporized chemical is selected from air, oxygen rich gas or pure oxygen;
Described three runner spraying guns (30) are a kind of telescoping structures, it is made up of centre channel (63), interior ring passage (64) and outer ring channel (65), described centre channel (63) and outer ring channel (65) are the vaporized chemical passages, ring passage (64) is the hydrocarbon substance-containing slurry passage in described, and described hydrocarbon substance-containing slurry and described vaporized chemical carry out thorough mixing in three runner spraying gun (30) exits and well atomized;
Heat preserving type air-flow bed coal-gasification reactor (11) is a cylindrical tube in described, the top of this reactor (11) is reaction chamber, the bottom is a cooling room, its reaction chamber is interior heat-preserved and heat-insulated, wash away the erosive material and make with standing high-temperature ash near the internal layer of reaction chamber, the middle layer is that usefulness can play heat-blocking action, prevents that the material of calorific loss from making, skin near reactor (11) housing is to have used insulation effect, and the material of reduction case temperature is made; Described cooling room is provided with water coolant sparger (34), telescopic inner core (31) and urceolus (32), inner core (31) upper end is connected and fixed with water coolant sparger (34), urceolus (32) is supported on the cooling room housing, adopts preset pieces to fix between the inner/outer tube (31,32);
C, the cooling of high temperature crude synthesis gas, bubbling water-bath cooling removes lime-ash: the high temperature crude synthesis gas and the high-temperature ash mixture that allow above-mentioned steps B obtain mix with the water coolant that enters described reactor (11) cooling room by described water coolant sparger (34), then, inner core (31) by described cooling room enters the bubbling water-bath (33) that is arranged in this reactor (11) cooling room bottom, through water quench, after bubbling water-bath (33) cooling removes lime-ash, the cinder slag is trapped in the bottom, the crude synthesis gas that contains a small amount of thin ash rises along the annular space between inner core (31) and the urceolus (32), increase owing to the space in the annular space exit suddenly, gas velocity significantly reduces, portion of water of carrying secretly in the crude synthesis gas and ash content are got back to bottom bubbling water-bath (33), and gas flows out described reactor (11) along outlet conduit (12);
D, cinder slag discharging: allow the cinder slag after water quench, bubbling water-bath (33) cooling remove lime-ash from above-mentioned steps C enter bottom cinder slag blowdown system, the cinder slag enters lock hopper (24) by lock slag valve (22), discharge by vent valves (25), the water in the cinder slag enters the vacuum evaporator (44) that contains thin grey water handing part;
E, crude synthesis gas cooling dedusting, washing, purifying: will or enter from the crude synthesis gas that contains a small amount of thin ash of above-mentioned steps C and remove the thin buck of wherein carrying secretly that contains in the air water separator (13), the thin buck of collecting that contains is sent to along pipeline (28) after reducing pressure and is carried out thin grey water handing, delivers to gas-water mixer (15) and remove the crude synthesis gas that contains thin buck along pipeline (14); Perhaps will directly deliver to gas-water mixer (15) without air water separator (13) from the crude synthesis gas that contains a small amount of thin ash of step C along pipeline (12); In gas-water mixer (15), this crude synthesis gas with from the buck thorough mixing of gas wash tower (17), the mixture of crude synthesis gas, water and a small amount of thin ash enters gas wash tower (17) by pipeline (16) then, arrive bubbling style water-bath storage tank (41) along downtake (39), after washing ash, rise along downtake (39) and upcast (40) annular space, and carry out multistage washing by eddy flow plate (38), traverse baffle (37) and tower tray (36), discharge obtains synthetic gas from gas wash tower (17) top along pipeline (26) by scum dredger (35) back then; The buck of bubbling style water-bath storage tank (41) enters grey water-circulating pump (19) along pipeline (18), behind grey water-circulating pump (19) pressure-raising, be divided into two-way, one curb pipeline (20) is sent into the thin ash in gas-water mixer (15) the infiltration crude synthesis gas, and the water coolant sparger (34) of heat preserving type air flow bed reactor (11) cinder notch below was as water coolant in another curb pipeline (21) was sent into;
F, contain thin grey water handing: this gas wash tower (17) bubbling style water-bath storage tank (41) bottom contains thin buck and contains thin buck and contain thin grey water handing along pipeline (28), the thin buck that contains of discharging from cooling room after pipeline (29) reduces pressure respectively along pipeline (27), air water separator (13) are isolating, at first enter high-temperature water heater (42) step-down cooling, the step-down escaping gas enters grey water-to-water heat exchanger (57) or reclaims hot-water tower (60) and reclaim heat; Concentrated after high-temperature water heater (42) step-down contains thin buck and enters low-temperature water heating device (43) and carry out step-down once more, escaping gas or directly enter degassing tank (55) as thermal source after the step-down perhaps is used as thermal source by entering de aerated water groove (55) after condenser (59) the heat exchange cooling; This low-temperature water heating device (43) bottom concentrates and contains thin buck and enter vacuum evaporator (44) and carry out step-down; Escaping gas enters negative pressure separator (46) after negative pressure condenser (58) cooling cooling in vacuum evaporator (44), enter off-gas pump (47) after separating moisture, emptying after off-gas pump separator (48) separates moisture again, the isolating water of isolating water of off-gas pump separator (48) and negative pressure separator (46) flows into aqua storage tank (52), and vacuum evaporator (44) bottom concentrates and contains thin buck enter clarifying tank (50) behind clarifying tank feeding pump (49) pressure-raising; In clarifying tank (50), add flocculation agent and make thin grey suspended substance flocculation, the top overflow water flows into aqua storage tank (52), all flow into buck part behind grey water pump (54) pressure-raising of aqua storage tank (52) and send into degassing tank (55), and a part is as wash-down water, and small part effluxes; In degassing tank (55), the gas dissolved of carrying secretly in circulation buck emptying after heating adds dispersion agent at degassing tank (55) water outlet or in degassing tank (55), simultaneously to alleviate the fouling of interchanger and ash-water pipeline; The circulation buck enters grey water-to-water heat exchanger (57) or reclaims hot-water tower (60) through degassing water pump (56) pressure-raising, with send into gas wash tower (17) middle and lower part import after high-temperature water heater (42) the escaping gas heat exchange temperature raising, arrive bubbling style water-bath storage tank (41) and recycle; Ash content higher concentrated in clarifying tank (50) bottom contains thin buck and enters vacuum band-type filter machine (51) through filter feeding pump (53) pressure-raising, in vacuum band-type filter machine (51) with thin ash and water sepn, thin ash is collected the back and is discharged, and isolated water comes back in the clarifying tank (50).
2, method according to claim 1 is characterized in that describedly containing that hydrocarbon material is selected from solid carbon-contg hydrogen material and/or liquid state contains hydrocarbon material; Described solid carbon-contg hydrogen material is one or more solid carbon-contg hydrogen materials that are selected from coal, petroleum pitch, coal liquefaction residue, refinery coke, biomass, municipal wastes, organic waste residues; It is that one or more are selected from residual oil, waste oil, the liquid state that contains hydrocarbon organic waste water, spent pulping liquor contains hydrocarbon material that described liquid state contains hydrocarbon material.
3, method according to claim 1 is characterized in that the described ratio that contains hydrocarbon material, water, auxiliary agent and additive is respectively in its material gross weight 56～80%, 18～40%, 0～4%, 0.2～0.4%.
4, method according to claim 1 is characterized in that described interior heat preserving type air-flow bed coal-gasification reactor (11) is a cylindrical tube, and its cylindrical shell height is 4～5 with the ratio of mean diameter.
5, method according to claim 1, it is characterized in that described interior heat preserving type air flow bed reactor (11) is provided with direct or indirect temperature measuring equipment, wherein the direct temperature measurement device is to insert pyrometer couple in reaction chamber, the front end of this thermopair with concordant near the reaction chamber inner layer material or in the 10～20mm that contracts, directly measure reaction chamber temperature; Temperature measuring equipment is to use pyrometer couple to detect casing surface temperature indirectly, judges the operation conditions of this reactor (11).
6, method according to claim 1, it is characterized in that described gas-water mixer (15) is made up of outer tube and center-aisle, center-aisle is a kind of throat tubular construction, crude synthesis gas enters from outer tube, the center-aisle trunnion is walked buck, return by gas wash tower (17) bottom bubbling style water-bath storage tank (41) in the trunnion exit and to enter grey water-circulating pump (19) along pipeline (18) and behind grey water-circulating pump (19) pressure-raising, to enter the buck and the crude synthesis gas thorough mixing of gas-water mixer (15) even, the thin ash in the crude synthesis gas is soaked into fully along pipeline (20).
7, method according to claim 1, it is characterized in that described gas wash tower (17) is a cylindrical overpressure resistant barrel, the middle part of going up of this washing tower is provided with scum dredger (35), tower tray (36) and traverse baffle (37), eddy flow plate (38), and the bottom is provided with gas downtake (39), upcast (40) and bubbling style water-bath storage tank (41).
8, method according to claim 1, it is characterized in that reclaiming heat and being or allowing the step-down escaping gas enter grey water-to-water heat exchanger (57) indirect heat exchange in described contain in the thin grey water handing, in grey water-to-water heat exchanger (57) to from the circulation buck heating of degassing tank (55) behind degassing water pump (56) pressure-raising, step-down effusion gas major part enters air water separator (45) after being condensed into liquid, its gas is discharged burning emptying or recycling from air water separator (45) top, isolated water is got back to degassing tank (55), and the circulation buck after the intensification enters gas wash tower (17) middle and lower part import; Perhaps allow the step-down escaping gas enter and reclaim hot-water tower (60) direct heat exchange, in reclaiming hot-water tower (60) to from the circulation buck heat temperature raising of degassing tank (55) through water pump (56) pressure-raising that outgases, the back small portion gas of self lowering the temperature is dissolved in the circulation buck again, by returning gas wash tower (17) middle and lower part import behind pressure-raising pump (61) pressure-raising, most of gas is discharged burning or is recycled from the top.
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