CN109437604A - The method for realizing calcine Exposure degree and waste gas utilization using methane reforming - Google Patents
The method for realizing calcine Exposure degree and waste gas utilization using methane reforming Download PDFInfo
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- CN109437604A CN109437604A CN201811347885.7A CN201811347885A CN109437604A CN 109437604 A CN109437604 A CN 109437604A CN 201811347885 A CN201811347885 A CN 201811347885A CN 109437604 A CN109437604 A CN 109437604A
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- Prior art keywords
- lime
- methane
- carbon dioxide
- gas
- calcine
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
A method of calcine Exposure degree and waste gas utilization are realized using methane reforming.It is passed through in kiln from bottom to top by methane and from the carbon dioxide of tail gas from limekiln lower part cooling zone, the sensible heat own temperature that methane and carbon dioxide absorbs calcine is gradually increased and plays the preliminary cooling effect to lime, reforming reaction occurs for methane and carbon dioxide in 700 DEG C to 1150 DEG C of temperature and area of space, reforming reaction absorbs a large amount of heat, and be superimposed with gaseous exchange heat exchange, realize the further rapid cooling of high temperature firing lime to improve its activity degree.Reformate of the present invention is the synthesis gas rich in carbon monoxide, hydrogen, can be used for the processes such as chemical industry synthesis, combustion power generation, reduction of iron ore, while the present invention realizes rapid cooling and the Exposure degree of calcine, reduces CO2 emission.It is the method simple process, at low cost, guaranteeing that limekiln efficiently produce and under the premise of lime high-quality, with preferable economic benefit and environmental benefit.
Description
Technical field
The present invention principally falls into Coal Clean and efficiently utilizes and energy conservation and environmental protection, and in particular to a kind of to utilize methane reforming
The method that calcine Exposure degree and Resources of Carbon Dioxide utilize is realized, for improving the lime quality in limekiln, reducing
Lime calcining process energy consumption and the resource utilization for realizing carbon dioxide in tail gas.
Background technique
Lime is important one of flux and slag making materials in steel production, China is major, medium-sized iron and steel enterprise substantially
There is the production facility of lime.To China's lime industry size in 2015 up to 2.5 hundred million tons, practical production capacity is 2.3 hundred million tons, it is contemplated that
To the year two thousand twenty, China's lime production capacity is by steady-state growth to 2.5 hundred million tons.With the promotion of China's smelting iron and steel technological level, lime
Production technology level also correspondinglys increase, selection, exploitation, transport, processing and type selecting, the improvement of kiln including lime stone etc..
But there are still energy consumptions it is high, discharge is big, product quality is uneven the problems such as.Lime stove evenly heat efficiency is and big less than 40%
Part is reached 145kg/t, is caused pollutant emission than more serious with coal main fuel, lime unit mark coal.Further, since lime roasts
Burning process raw mineral materials itself can give off great amount of carbon dioxide, along with the energy consumption of itself, lime commercial silica carbon emission
Amount accounts for 2% or more of the whole nation.Lime industry energy-saving and emission-reduction focus includes furnace kiln structure optimization, UTILIZATION OF VESIDUAL HEAT IN (tail gas, firing
Lime), kiln gas enrichment recycle etc. several aspects.
About the cooling of calcine, patent " lime kiln afterheat cooling system CN201120436645.1 " discloses one kind
Lime kiln afterheat cooling system, it is mainly cooling using air blower forced convertion, to improve the cooling velocity of limekiln discharge zone, add
Fast lime discharging, promotes lime production efficiency.This is the prevailing technology that current lime production uses, but carbon dioxide in tail gas
Concentration is lower, and Resources of Carbon Dioxide is big, at high cost using difficulty.
About the recycling of waste heat from tail gas, patent " a kind of beam-type limekiln residual neat recovering system CN201610547868.2 ",
" limekiln waste heat from tail gas utilizes system CN201620779912.8 ", " fuel gas preheating device of gas based on gas burning lime kiln tail gas
CN201220221618.7 " etc. discloses waste heat from tail gas recovery method similar in principle, preheats for coal gas, combustion air,
Or cogeneration is carried out, so that limekiln lower power consumption, increases economic efficiency.But this kind of waste heat recycling does not account for waste heat
Quality benefit, i.e. high-quality sensible heat and low-quality sensible heat, which are mixed, to be recycled, and the money of carbon dioxide in tail gas is not accounted for yet
Source Utilizing question.
Carbon dioxide mass fraction is relatively low (about 18%~25%) in conventional lime kiln exhaust gas, and impurity is more in component, therefore,
When recycling, it is necessary to remove the impurity such as chalk dust removing first, then be purified, investment and operating cost are compared with industries such as petrochemical industry chemical industry
It is high.Nevertheless, splendid steel had built pressure-variable adsorption once and hot potassium method absorbs 2 covering devices, former in the mid-90 in last century
Upper five factory of steel had also once built limekiln carbon dioxide recovering apparatus.The steel subsidiary factory that Baosteel creates in Zhanjiang at present, by stone
The recycling of carbon dioxide is included among overall construction plan in grey kiln exhaust gas, and Taiyuan Iron and Steel Co., Anshan iron and steel plant have all started CO_2 Resource
The investigation of recycling and feasibility study work.
Based on sleeve lime kiln, in order to make tail gas enrichment method, carbon dioxide circulatory mediator is proposed in recent years and is followed
Ring roasts limekiln (such as patent " a kind of lime kiln device CN201810438781.0 using circulating air ", a kind of " limekiln
Flue gas recirculation system CN201810221778.3 "), above-mentioned carbon dioxide enriched mesh can also be realized by using pure oxygen burning
's.There is problems in that how to realize the rapid cooling of firing high temperature quick lime.If doing cooling air using carbon dioxide, having can
Quick lime can be caused to regenerate calcium carbonate；If cooling using conventional air, gas concentration lwevel is again by significantly dilute in tail gas
It releases.In order to guarantee the implementation of lime-roasting new process, there is an urgent need to invent the cooling technique of new calcine.
Summary of the invention
The circulation for doing circulatory mediator for carbon dioxide or high carbon dioxide concentration flue gas roasts limekiln, and the present invention will solve
Certainly the technical issues of includes: the production of active lime other than guaranteeing uniform and stable roasting, also needs to consider how to realize high
Warm (about 1150 DEG C) firing quick limes are quickly cooled to 700 DEG C or less to guarantee its high activity；On the basis of realizing cooling, how
Realize that the high efficiente callback of lime sensible heat utilizes；On the basis of realizing that lime is cooling, the tail gas of high carbon dioxide concentration how is obtained,
Dioxy chemical conversion is avoided to react with calcine simultaneously.Therefore, it is necessary to the cooling technique technology of new calcine is developed, and
It is able to achieve the recycling of heat, while facilitating the resource utilization of tail gas, to realize that the efficient and energy saving of lime manufacturing process subtracts
Row.
The invention proposes a kind of sides that calcine Exposure degree and tail gas resource utilization are realized using methane reforming
Method, it is characterised in that methane and carbon dioxide is passed through in kiln from bottom to top from limekiln lower part cooling zone, utilizes methane reforming
Endothermic heat of reaction realizes cooling and the Exposure degree of calcine, and products obtained therefrom is high-quality quick lime and is rich in carbon monoxide, hydrogen
The synthesis gas of gas.
The present invention is achieved by the following technical solutions:
(1) by after room temperature or preheating carbon dioxide, methane from limekiln lower part adverse current be passed through, carbon dioxide, methane by
Edge up temperature, and the temperature of lime is gradually reduced, and the temperature of lime is higher than the temperature for being passed through gas, the volume flow of carbon dioxide and methane
Measure it is identical, unstrpped gas total flow be 40~80m3/ t lime.
(2) when unstrpped gas temperature reaches 700 DEG C, it is enabled to interact with supported catalyst, carbon dioxide and methane
It is converted into carbon monoxide and hydrogen, every cubic metre of unstripped gas absorbs the heat of 5000~6000kJ simultaneously, and the temperature of lime is corresponding
Decline rapidly forms the high-quality product that activity degree is greater than 320.
Further, carbon dioxide used is from lime kiln exhaust gas, the mixed raw material gas of carbon dioxide and methane composition
Enter in kiln from limekiln lower part through heat exchange pipeline and exchange heat, regulates and controls heat exchange rate by adjusting caliber and the shape of heat exchanger tube,
Pipeline positioned at 700~1150 DEG C of regions is provided with the cellular porous material of aluminum oxide, and load has reformation to urge in porous material
Agent.
Further, resulting gas can be used for the processes such as chemical industry synthesis, combustion power generation, reduction of iron ore after reformation, can
By improving H with coke-stove gas mixing preparation2/ CO is to improve its efficiency for being used for chemical industry synthesis and reduction of iron ore.
Advantageous effects of the invention:
The invention can ensure that carbon dioxide does the smooth implementation of the circulation roasting limekiln new process of circulatory mediator, realizes and burn
At the rapid cooling of high temperature quick lime, the quick lime of high activity degree and the tail gas of high carbon dioxide concentration are obtained, to reduce dioxy
Change carbon cost for purification and its later use provides possibility.It is high realizing meanwhile by the reforming reaction of methane and carbon dioxide
While the rapid cooling of warm quick lime, the reformation gas of high carbon monoxide and density of hydrogen is obtained, the sensible heat of lime has been recycled.It should
The sensible heat of technique recycling accounts for 50% or so of the total sensible heat of calcine, and the carbon dioxide of resource utilization accounts for limestone calcination decomposition
Discharge 10% or so of total carbon dioxide capacity.The present invention is substantially that the high temperature sensible heat of calcine is converted to the change for reforming gas
Learn energy, while fixed part carbon dioxide.Present invention process is easy to implement and promotes, at low cost, efficiently gives birth in guarantee limekiln
Under the premise of producing with lime high-quality, there is preferable economic benefit and environmental benefit.
Detailed description of the invention
Fig. 1 is the stream for realizing calcine Exposure degree and waste gas utilization method in the embodiment of the present invention using methane reforming
Journey schematic diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
The present invention can also be understood completely in description.
Embodiment 1
The circulation for doing circulatory mediator for 1000 tons of carbon dioxide of daily output roasts limekiln, the methane and titanium dioxide of room temperature
Carbon mixed raw material gas enters limekiln cooled region from the pipeline near the bottom discharging mouth of limekiln, and total gas flow rate is
40m3/ t lime.The caliber of air inlet pipeline is gradually thicker to increase heat exchange area with the increase for entering kiln body depth.Air inlet
Pipeline is brought out outside kiln body when terminating height close to lime-roasting fastly, about 1150 DEG C of position.700 in pipeline~
For 1150 DEG C of section filling aluminum oxide honeycomb porous material to increase heat exchange area, which is also methane and carbon dioxide hair
The region of raw reforming reaction.Close to 80%, the gas after reformation is expelled from kiln gas conversions by pipeline, gained gas stream
Amount is 76m3/ t lime is used for the unstripped gas of synthesizing methanol through exchanging heat to 220 DEG C or so.Gained gas componant such as table 1 after reformation
Shown, the heat of recycling can be used for producing vapor.The activity degree of gained lime is 340.Discovery filling after long-play
There are a degree of analysis carbon close to high-temperature area for aluminum oxide honeycomb porous material.
1 reformed gas ingredient of table
Embodiment 2
Limekiln (fuel is coal gas of converter) is roasted for 1000 tons of daily output of pure oxygen burning, is preheated to 200 DEG C of methane
Enter limekiln cooled region from the pipeline near the bottom discharging mouth of limekiln with carbon dioxide mix unstrpped gas, gas always flows
Amount is 80m3/ t lime.The caliber of air inlet pipeline is gradually thicker to increase heat exchange area with the increase for entering kiln body depth.
Air inlet pipeline is brought out outside kiln body when terminating height close to lime-roasting fastly, about 1150 DEG C of position.700 in pipeline
~1150 DEG C of section filling carries the aluminum oxide honeycomb porous material of nickel-base catalyst to increase heat exchange area and promote weight
Turn over.Close to 96%, the gas after reformation is expelled from kiln gas conversions by pipeline, and gained gas flow is 157m3/
T lime is exchanged heat to 220 DEG C or so, and supplements carbon dioxide content to the unstripped gas after 5%, for synthesizing methanol.After reformation
Gained gas componant is as shown in table 1, and the heat of recycling can be used for preheating methane and carbon dioxide gas.The activity degree of gained lime
It is 360.Occur after long-play without analysis carbon phenomenon.
2 reformed gas ingredient of table
Claims (3)
1. a kind of method for realizing calcine Exposure degree and waste gas utilization using methane reforming, it is characterised in that by methane and
Carbon dioxide is passed through in kiln from bottom to top from limekiln lower part cooling zone, is absorbed heat using methane reforming reaction and is realized calcine
Cooling and Exposure degree, products obtained therefrom are high-quality quick lime and the synthesis gas rich in carbon monoxide, hydrogen；
Main production process are as follows:
(1) by after room temperature or preheating carbon dioxide, methane from limekiln lower part adverse current be passed through, carbon dioxide, methane gradually rise
The temperature of temperature, lime is gradually reduced, and the temperature of lime is higher than the temperature for being passed through gas, the volume flow phase of carbon dioxide and methane
Together, unstrpped gas total flow is 40~80m3/ t lime；
(2) when unstrpped gas temperature reaches 700 DEG C, it is enabled to interact with supported catalyst, carbon dioxide and methane conversion
For carbon monoxide and hydrogen, every cubic metre of unstripped gas absorbs the heat of 5000~6000kJ simultaneously, and the temperature of lime is accordingly rapid
Decline forms the high-quality product that activity degree is greater than 320.
2. a kind of method for realizing calcine Exposure degree and waste gas utilization using methane reforming according to claim 1,
It is characterized in that, carbon dioxide used is from lime kiln exhaust gas, the mixed raw material gas of carbon dioxide and methane composition is from lime
Kiln lower part enters in kiln through heat exchange pipeline to exchange heat, and regulates and controls heat exchange rate by adjusting caliber and the shape of heat exchanger tube, is located at 700
The pipeline in~1150 DEG C of regions is provided with the cellular porous material of aluminum oxide, and load has reforming catalyst in porous material.
3. a kind of method for realizing calcine Exposure degree and waste gas utilization using methane reforming according to claim 1,
It is characterized in that, reform after resulting gas can be used for chemical industry synthesis, combustion power generation, reduction of iron ore process, can by with coke
Producer gas mixing preparation improves H2/ CO is to improve its efficiency for being used for chemical industry synthesis and reduction of iron ore.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811347885.7A CN109437604B (en) | 2018-11-13 | 2018-11-13 | Method for realizing sensible heat recovery and tail gas utilization of burnt lime by utilizing methane reforming |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811347885.7A CN109437604B (en) | 2018-11-13 | 2018-11-13 | Method for realizing sensible heat recovery and tail gas utilization of burnt lime by utilizing methane reforming |
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| CN109437604A true CN109437604A (en) | 2019-03-08 |
| CN109437604B CN109437604B (en) | 2020-09-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333029A (en) * | 2020-02-29 | 2020-06-26 | 太原理工大学 | Process for reforming and reducing iron and generating carbon nano tube by methane and carbon dioxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090186952A1 (en) * | 2005-06-14 | 2009-07-23 | Andre Peter Steynberg | Process for the Preparation and Conversion of Synthesis Gas. |
| US20120101323A1 (en) * | 2008-07-16 | 2012-04-26 | Kellogg Brown & Root Llc | Systems and methods for producing substitute natural gas |
| US20120267577A1 (en) * | 2009-10-24 | 2012-10-25 | Calix Limited | System and method for processing an input fuel gas and steam to produce carbon dioxide and an output fuel gas |
| CN103787277A (en) * | 2014-01-15 | 2014-05-14 | 中钢集团鞍山热能研究院有限公司 | Method and device for producing synthesis gas through methane reforming with blast furnace slag sensible heat |
-
2018
- 2018-11-13 CN CN201811347885.7A patent/CN109437604B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090186952A1 (en) * | 2005-06-14 | 2009-07-23 | Andre Peter Steynberg | Process for the Preparation and Conversion of Synthesis Gas. |
| US20120101323A1 (en) * | 2008-07-16 | 2012-04-26 | Kellogg Brown & Root Llc | Systems and methods for producing substitute natural gas |
| US20120267577A1 (en) * | 2009-10-24 | 2012-10-25 | Calix Limited | System and method for processing an input fuel gas and steam to produce carbon dioxide and an output fuel gas |
| CN103787277A (en) * | 2014-01-15 | 2014-05-14 | 中钢集团鞍山热能研究院有限公司 | Method and device for producing synthesis gas through methane reforming with blast furnace slag sensible heat |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333029A (en) * | 2020-02-29 | 2020-06-26 | 太原理工大学 | Process for reforming and reducing iron and generating carbon nano tube by methane and carbon dioxide |
| CN111333029B (en) * | 2020-02-29 | 2023-03-28 | 太原理工大学 | Process for reforming and reducing iron and generating carbon nano tube by methane and carbon dioxide |
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