CN104263416A - Method for preventing slagging of catalytic gasification furnace - Google Patents

Method for preventing slagging of catalytic gasification furnace Download PDF

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Publication number
CN104263416A
CN104263416A CN201410549576.3A CN201410549576A CN104263416A CN 104263416 A CN104263416 A CN 104263416A CN 201410549576 A CN201410549576 A CN 201410549576A CN 104263416 A CN104263416 A CN 104263416A
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China
Prior art keywords
coal
temperature
slagging
sample
catalytic gasification
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CN201410549576.3A
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Chinese (zh)
Inventor
毕继诚
芦涛
李克忠
张�荣
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Priority to CN201410549576.3A priority Critical patent/CN104263416A/en
Publication of CN104263416A publication Critical patent/CN104263416A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a method for preventing slagging of a catalytic gasification furnace. The method comprises the following steps: mixing high catalyst loaded easily slagged coal, which is used as a raw material, with water washing slag to prepare a sample, and gasifying the prepared sample in a fluidized bed, wherein in the sample, the high catalyst loaded easily slagged coal content is 80-95 wt% and the water washing slag content is 5-20 wt%. The method has the advantages that the method is simple and practical, the added amount of the water washing slag can be adjusted as needed to increase the melting point and sintering temperature of coal ash, and the requirement of application of the high catalyst loaded coal to a catalytic gasification process is met.

Description

A kind of method of preventing catalytic gasification Slagging in Texaco Gasifier
Technical field
The present invention relates to a kind of method of preventing catalytic gasification Slagging in Texaco Gasifier.
Background technology
In today that global economy develops rapidly, contradiction between oil supply and demand becomes increasingly conspicuous, and China's oil importation dependence is more and more higher, and serious threat is to Chinese energy safety and economic construction.Seek new substitute energy imperative, Coal Chemical Industry more and more demonstrates advantage.Gasification of coal has had the history of more than 200 year.Gasification of coal is an integral part of coal conversion technology, is one of important technology of clean, efficiency utilization coal.By catalyst effect, temperature of reaction can be reduced, improve speed of response, improve coal gas composition, improve calorific value, cause the extensive concern of people.According to the developing direction of clean coal technology and the development trend of world's low-carbon economy; utilize the coal that china natural resources advantage is relatively large; especially the low-grade coal such as brown coal is by catalytic gasification production substitute natural gas; efficient, the clean utilization of coal can not only be promoted; and with lower economic cost; the imbalance between supply and demand of effective alleviation Sweet natural gas is applicable China's national situation, dissolve energy dilemma and ensure the effective way of energy security.
The catalytic gasification of coal is a kind of advanced gasification process reducing temperature of reaction, improve speed of reaction, improve gas composition, and catalytic coal gasifaction introduces can the C-H of catalysis simultaneously 2o gasification reaction, water gas shift reaction and CO/H 2the catalyzer of methanation reaction, generates the synthetic gas being rich in methane under lesser temps (650-750 DEG C), elevated pressures (3.0-4.0MPa) condition in pressurized fluidized bed gasifier.In catalytic gasification process, need to add a certain amount of alkali (alkaline earth) salt as catalyzer, these alkali of fluxing (alkaline earth) salt catalysts can make the melt temperature of coal ash reduce, at high temperature can aggravate coal ash particle mutually to reunite slagging scorification, time serious, deslagging difficulty, even defluidization etc., cause reactor to be difficult to continuous and steady operation.
Summary of the invention
Instant invention overcomes above-mentioned technical deficiency part, its object is to provide a kind of method preventing catalytic gasification Slagging in Texaco Gasifier, the method is simple and practical, the amount adding washing slag can be regulated as required to improve coal ash fusion temperature and sintering temperature, meet the application of coal in catalysis gasification technique of high capacity catalyzer.
Above-mentioned purpose of the present invention is achieved through the following technical solutions.
A kind of method of preventing catalytic gasification Slagging in Texaco Gasifier, it with the clinker(ing) coal of high capacity catalyzer for raw material, the washing slag mixing self mixes sample, in sample, the clinker(ing) coal content of high capacity catalyzer is 80-95wt%, washing slag content is 5-20wt% (mass percent), and the sample prepared gasifies in fluidized-bed.
In the clinker(ing) coal of high capacity catalyzer as above, catalyst loadings is 8-20wt%, and its sintering temperature is below 700 DEG C.
Clinker(ing) coal as above is the coal sample that coal ash fusion temperature temperature is less than 1200 DEG C, as king family's tower coal, and Erdos coal etc.
Catalyzer as above is alkali metal compound, as K 2cO 3, KOH, Na 2cO 3, Li 2cO 3deng.
Gasification condition as above is that fluidized-bed carries out the known condition that gasifies, temperature of reaction 650 DEG C-750 DEG C, reaction pressure 3-4 MPa, and the residence time is 1-3h, steam atmosphere.
Also containing refractories such as a large amount of Si, Al in the lime-ash of supported catalyst coal, be also rich in the flux material such as K, Ca, Fe simultaneously, if lime-ash is after washing process, the flux material such as most of K, the Ca in coal ash can be made to remove, thus make SiO 2and Al 2o 3there is enrichment.Lime-ash after washing is added in raw coal, the chemical composition of raw coal ash and mineral composition are changed, thus make the sintering temperature of high capacity catalyzer coal exceed service temperature in stove, prevent slagging scorification.
The present invention has the following advantages:
(1) self coal solves the clogging problems of self, does not need to add other external material.(1) recycling of lime-ash.(3) the washing lime-ash added is to the efficiency of carbon conversion of high capacity catalyzer coal, and catalyst recovery yield can not make a big impact.(4) the present invention can be widely used in the independent gasification of coal, biomass (comprising rubbish etc.) etc. or the common gasification of burning and coal and biomass and catalytic gasification.
Accompanying drawing explanation
Fig. 1 is king family tower coal sample load 20%K 2cO 3catalyzer gasification slag.Fig. 2 is king family tower coal sample load 20%K 2cO 3catalyzer adds the gasification slag after the washing slag of 10%.Fig. 3 is Erdos coal sample load 10%K 2cO 3catalyzer gasification slag.Fig. 4 is Erdos coal sample load 10%K 2cO 3catalyzer adds the gasification slag after the washing slag of 8%.Fig. 5 is king family tower coal load 10%K 2cO 3the determination figure of sintering temperature.
Embodiment:
The sintering of coal ash refers to the bonding of adjacent powdered granule under the effect of excessive surface free energy, after the heating of solid state powder aggregation, under the high temperature lower than its fusing point or eutectic point, pore is got rid of, volumetric shrinkage, becomes the fine and close multicrystal process with some strength.Sintering is a spontaneous and irreversible process, and it is promote to sinter the basic motive of carrying out that system surfaces can reduce.Powder granule specific surface area is larger, and its surface energy had is also higher, and according to least-energy principle, it will spontaneously to minimum energy change of state, and the surface energy of simultaneity factor reduces.Along with the carrying out of coal ash sintering, the closed pores between coal ash particle diminishes, and open bore becomes large, defines new passage gradually.When coal ash sintering occur time, gray columns can shrink, between gray columns and pipeline and gray columns inside can form new gas passage, thus cause pressure reduction to reduce, so when there is sintering, pressure reduction variation with temperature curve has individual weight break point, temperature corresponding to this point is the sintering temperature of coal ash.The determination of ash application pressure decline method sintering temperature as shown in Figure 5.Fig. 5 is king family tower coal load 10%K 2cO 3the determination figure of sintering temperature, as can be seen from the figure, when temperature is more than 650 DEG C, pressure reduction declines rapidly, illustrates that at this moment coal ash starts to sinter, thus judges that the sintering temperature of this coal ash is as 650 DEG C.
The present invention is described in detail as follows in conjunction with the embodiments:
Embodiment 1
(1) be in king family's tower coal sample of 1177 DEG C in ash fusion point, with coal sample and K 2cO 3catalyst solution carries out dip loading for 1:1 by volume, makes K in supported catalyst king family tower coal sample 2cO 3catalyst loadings is 20wt%.
(2), after supported catalyst in king family's tower coal sample, washing slag 10wt% is mixed by the mode of mechanically mixing.
(3) step (1) is prepared sample in fluidized-bed, temperature of reaction 650 DEG C, reaction pressure 3MPa, the residence time is 1h, gasify under steam atmosphere, occur obvious caking phenomenon, sintering temperature is 580 DEG C, the gas group prejudice table 1 after gasification.
(4) step (2) is prepared sample in fluidized-bed, temperature of reaction 650 DEG C, reaction pressure 3MPa, the residence time is 1h, gasify under steam atmosphere, slagging scorification phenomenon be improved significantly, sintering temperature is 670 DEG C, higher than the service temperature in fluidized-bed.Gas group prejudice table 1 after gasification.
Embodiment 2
(1) be in king family's tower coal sample of 1177 DEG C in ash fusion point, with coal sample and K 2cO 3catalyst solution carries out dip loading for 1:1 by volume, makes K in supported catalyst king family tower coal sample 2cO 3catalyst loadings is 15wt%.
(2), after supported catalyst in king family's tower coal sample, washing slag 8wt% is mixed by the mode of mechanically mixing.
(3) step (1) is prepared sample in fluidized-bed, temperature of reaction 700 DEG C, reaction pressure 3.5MPa, the residence time is 2h, gasify under steam atmosphere, occur Serious Slagging phenomenon, sintering temperature is 610 DEG C, the gas group prejudice table 1 after gasification.
(4) step (2) is prepared sample in fluidized-bed, temperature of reaction 700 DEG C, reaction pressure 3.5MPa, the residence time is 2h, gasify under steam atmosphere, there is not caking phenomenon in lime-ash, sintering temperature is 765 DEG C, higher than the service temperature in fluidized-bed.Gas group prejudice table 1 after gasification.
Embodiment 3
(1) be in king family's tower coal sample of 1177 DEG C in ash fusion point, with coal sample and Na 2cO 3catalyst solution carries out dip loading for 1:1 by volume, makes Na in supported catalyst king family tower coal sample 2cO 3catalyst loadings is 8wt%.
(2), after supported catalyst in king family's tower coal sample, washing slag 5wt% is mixed by the mode of mechanically mixing.
(3) step (1) is prepared sample in fluidized-bed, temperature of reaction 750 DEG C, reaction pressure 4MPa, the residence time is 3h, gasify under steam atmosphere, occur Serious Slagging phenomenon, sintering temperature is 685 DEG C, the gas group prejudice table 1 after gasification.
(4) step (2) is prepared sample in fluidized-bed, temperature of reaction 750 DEG C, reaction pressure 4MPa, the residence time is 2h, gasify under steam atmosphere, slagging scorification phenomenon be improved significantly, sintering temperature is greater than 800 DEG C, higher than the service temperature in fluidized-bed.Gas group prejudice table 1 after gasification.
Embodiment 4
(1) be in the Erdos coal sample of 1062 DEG C in ash fusion point, with coal sample and K 2cO 3catalyst solution carries out dip loading for 1:1 by volume, makes K in supported catalyst king family tower coal sample 2cO 3catalyst loadings is 20wt%.
(2), after supported catalyst in king family's tower coal sample, washing slag 10wt% is mixed by the mode of mechanically mixing.
(3) step (1) is prepared sample in fluidized-bed, temperature of reaction 650 DEG C, reaction pressure 3MPa, the residence time is 1h, gasify under steam atmosphere, occur obvious caking phenomenon, sintering temperature is 560 DEG C, the gas group prejudice table 1 after gasification.
(4) step (2) is prepared sample in fluidized-bed, temperature of reaction 650 DEG C, reaction pressure 3MPa, the residence time is 1h, gasify under steam atmosphere, slagging scorification phenomenon be improved significantly, sintering temperature is 660 DEG C, higher than the service temperature in fluidized-bed.Gas group prejudice table 1 after gasification.
Embodiment 5
(1) be in the Erdos coal sample of 1062 DEG C in ash fusion point, with coal sample and K 2cO 3catalyst solution carries out dip loading for 1:1 by volume, makes K in supported catalyst king family tower coal sample 2cO 3catalyst loadings is 15wt%.
(2), after supported catalyst in king family's tower coal sample, washing slag 8wt% is mixed by the mode of mechanically mixing.
(3) step (1) is prepared sample in fluidized-bed, temperature of reaction 700 DEG C, reaction pressure 3.5MPa, the residence time is 2h, gasify under steam atmosphere, occur Serious Slagging phenomenon, sintering temperature is 600 DEG C, the gas group prejudice table 1 after gasification.
(4) step (2) is prepared sample in fluidized-bed, temperature of reaction 700 DEG C, reaction pressure 3.5MPa, the residence time is 2h, gasify under steam atmosphere, there is not caking phenomenon in lime-ash, sintering temperature is 745 DEG C, higher than the service temperature in fluidized-bed.Gas group prejudice table 1 after gasification.
Embodiment 6
(1) be in the Erdos coal sample of 1062 DEG C in ash fusion point, with coal sample and Na 2cO 3catalyst solution carries out dip loading for 1:1 by volume, makes Na in supported catalyst king family tower coal sample 2cO 3catalyst loadings is 8wt%.
(2), after supported catalyst in king family's tower coal sample, washing slag 5wt% is mixed by the mode of mechanically mixing.
(3) step (1) is prepared sample in fluidized-bed, temperature of reaction 750 DEG C, reaction pressure 4MPa, the residence time is 3h, gasify under steam atmosphere, occur Serious Slagging phenomenon, sintering temperature is 660 DEG C, the gas group prejudice table 1 after gasification.
(4) step (2) is prepared sample in fluidized-bed, temperature of reaction 750 DEG C, reaction pressure 4MPa, the residence time is 2h, gasify under steam atmosphere, slagging scorification phenomenon be improved significantly, sintering temperature is 780 DEG C, higher than the service temperature in fluidized-bed.Gas group prejudice table 1 after gasification.
Be more than preferred embodiment of the present invention, the unsubstantiality that every technical solution of the present invention is done improves, and when the function produced does not exceed the scope of technical solution of the present invention, all belongs to protection scope of the present invention.
Table 1

Claims (6)

1. prevent a method for catalytic gasification Slagging in Texaco Gasifier, it is characterized in that comprising the steps:
With the clinker(ing) coal of high capacity catalyzer for raw material, the washing slag mixing self mixes sample, and in sample, the clinker(ing) coal content of high capacity catalyzer is 80-95wt%, and washing slag content is 5-20wt%, and the sample prepared gasifies in fluidized-bed.
2. a kind of method of preventing catalytic gasification Slagging in Texaco Gasifier as claimed in claim 1, it is characterized in that in the clinker(ing) coal of described high capacity catalyzer, catalyst loadings is 8-20wt%, its sintering temperature is below 700 DEG C.
3. a kind of method of preventing catalytic gasification Slagging in Texaco Gasifier as claimed in claim 2, is characterized in that described clinker(ing) coal is the coal that coal ash fusion temperature temperature is less than 1200 DEG C.
4. a kind of method of preventing catalytic gasification Slagging in Texaco Gasifier as claimed in claim 3, is characterized in that the coal that coal ash temperature is less than 1200 DEG C is king family's tower coal or Erdos coal.
5. a kind of method of preventing catalytic gasification Slagging in Texaco Gasifier as claimed in claim 1, is characterized in that described catalyzer is alkali metal compound, as K 2cO 3, KOH, Na 2cO 3or Li 2cO 3.
6. a kind of method of preventing catalytic gasification Slagging in Texaco Gasifier as claimed in claim 1, is characterized in that described gasification condition gasifies at fluidized-bed, temperature of reaction 650 DEG C-750 DEG C, reaction pressure 3-4 MPa, and the residence time is 1-3h, steam atmosphere.
CN201410549576.3A 2014-10-16 2014-10-16 Method for preventing slagging of catalytic gasification furnace Pending CN104263416A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106167720A (en) * 2016-07-21 2016-11-30 新奥科技发展有限公司 The catalysis gasification method of a kind of high ferro coal and system

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WO2006082543A1 (en) * 2005-02-01 2006-08-10 Sasol-Lurgi Technology Company (Proprietary) Limited Method of operating a fixed bed dry bottom gasifier
CN101921644A (en) * 2010-07-30 2010-12-22 中国神华能源股份有限公司 Method for improving coal ash melting temperature by utilizing aluminium oxide as additive
CN103992822A (en) * 2014-05-16 2014-08-20 新奥科技发展有限公司 Catalytic gasification method and device
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* Cited by examiner, † Cited by third party
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CN106167720A (en) * 2016-07-21 2016-11-30 新奥科技发展有限公司 The catalysis gasification method of a kind of high ferro coal and system

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Application publication date: 20150107