CN103937520B - For the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio - Google Patents
For the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio Download PDFInfo
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Abstract
The invention discloses a kind of for the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio, method described in it is added in as-fired coal by powder particle size≤80 object carbonate benefit carbon raw material to mix, obtain mixture charge, mixture charge is loaded gas retort heating, then furnace charge is down to normal temperature through quenching operation, solid cleaning fuel is, the CO of generation again after screening
2the H with surplus in carbonization gas is directly entered with CO gas
2gas coupling carries out benefit carbon, and the metal oxide of carbonate decomposition by-product enters in produced solid cleaning fuel, control SO in combustion
2discharge.Carbonate mineral directly adds in destructive distillation as-fired coal by the present invention, utilizes the CO that thermolysis produces
2be that dry distillation gas mends carbon with CO gas, there is abundant raw material source, technological process is simple, low equipment investment, benefit carbon cost are low, the feature such as good economy performance, height can be widely used in, medium temperature carbonization coal gas mends carbon.
Description
Technical field
The present invention relates to a kind of method regulating dry distillation gas hydrogen-carbon ratio, specifically a kind of method regulating dry distillation gas hydrogen-carbon ratio for coal gas retort.
Background technology
Coal burning is that the long duration obtains the major way of the energy at present and even from now in China, and the direct burning of a large amount of coal, causes China's air environmental pollution serious, haze weather takes place frequently, simultaneously not yet in effectly utilize chemical in coal, waste is serious, causes process economics poor.Therefore implement destructive distillation (plug) to using coal, fully reclaim contained chemical in coal, efficient cascade utilization coal aspect in the field of business forms extensive common recognition.
Coal carbonization gas is after recovery of chemical products, and main component is H
2, CH
4, CO, CO
2, N
2, C
mh
ndeng, can be used for production synthetic natural gas (SNG) or natural gas liquids (LNG) through the operation such as deep purifying, methanation; Or can be used for again methanol, synthesis wet goods through operations such as deep purifying, alkane transformations and synthesis, thus improve the added value of dry distillation gas, dry distillation gas is effectively used.But no matter be high temperature carbonization coal gas, or medium temperature carbonization coal gas, all there is H
2content is superfluous, and hydrogen-carbon ratio does not meet the mol ratio requirement of synthetic gas.Metallurgical coke as existing high temperature carbonization technology is produced, H in its dry distillation gas
2content reaches more than 50%, and carbon content is about 10%, and hydrogen-carbon ratio is up to more than 5; For another example the blue charcoal of existing medium temperature carbonization technology is produced, H in its dry distillation gas
2content reaches more than 40%, and hydrogen-carbon ratio reaches more than 3.5.
For the exess of H2 gas complete reaction must be carried out benefit carbon to dry distillation gas.Normally adopting gasification of coal to mend carbon, for reducing the nitrogen content in synthetic gas, needing empty point pure oxygen processed as vaporized chemical.As existing fixed bed pure oxygen gasification mends carbon technique, with coke or hard coal for raw material, pure oxygen, CO
2or water vapour is vaporized chemical, need supporting pure oxygen production equipment and pressure-variable adsorption (PSA) device; For another example larger Texaco's bed pulverized coal gasification technology, the investment of separate unit stove reaches several hundred million unit, and need join larger air separation facility, and feed coal requires very high.
Above-mentioned existing benefit carbon technique, complex process, one-time investment is very large, more difficult in China's dry distillation of coal business enterprise expand application.
Summary of the invention
The concrete technical problems that the present invention will solve is using carbonate minerals as benefit carbon raw material, directly add in destructive distillation as-fired coal material, by thermolysis, benefit carbon is carried out to dry distillation gas, its objective is provide that a kind of technique is simple, less investment and cost low for the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio.
To achieve these goals, the measure taked of the present invention is as follows:
For the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio, method described in it follows these steps to carry out:
(1) determine that the quality index of as-fired coal is: FC
d>=50%, V
adf>=25%, A
d≤ 25%, S
td< 1.5%;
(2) determine the burn out rate of carbonate benefit carbon raw material, the factor of created gase of as-fired coal and the composition of former dry distillation gas;
(3) dried carbonate is mended carbon raw material through thick broken, dry grinding, make powder particle size≤80 order;
(4) ground carbonate benefit carbon raw material is added in as-fired coal and mixes, obtain mixture charge, mixture charge is loaded gas retort;
Medium temperature carbonization, it is 0.5 ~ 28wt% of furnace coal weight that carbonate mends carbon raw material add-on;
High temperature carbonization, it is 4 ~ 30wt% of furnace coal weight that carbonate mends carbon raw material add-on;
(5) the mixture charge in gas retort is completely cut off air heating, carry out benefit carbon by thermolysis;
Medium temperature carbonization continuous heating 6 ~ 12h, furnace charge core temperature rises to 700 ~ 900 DEG C gradually;
High temperature carbonization continuous heating 12 ~ 24h, furnace charge core temperature rises to 900 ~ 1100 DEG C gradually;
Then be down to normal temperature through quenching operation after being come out of the stove by red heat furnace charge, then through screening, namely obtain solid cleaning fuel;
(6) the waste dry distillation gas that overflows of gas retort heat-processed, through tar removing, wet desulphurization, wash ammonia, wash the recovery of chemical products operation of benzene after, be the clean dry distillation gas after mending carbon; Its foreign matter content: tar≤0.02g/m
3, H
2s≤0.2g/m
3, NH
3≤ 0.05g/m
3, benzene≤4g/m
3;
The hydrogen-carbon ratio of the clean dry distillation gas after gained mends carbon is: R=(H
2-CO
2)/(CO+CO
2)=0.5 ~ 3.3.
Further, its supplementary technology scheme is as follows.
Described carbonate mends the add-on of carbon raw material by following formulae discovery:
Wherein: M
s---the burn out rate of carbonate, wt%;
V
r---dry as-fired coal factor of created gase, Nm
3/ t;
V
cO---the percentage by volume of CO gas in former dry distillation gas composition, V%;
V
cO2---CO in former dry distillation gas composition
2the percentage by volume of gas, V%;
V
h2---H in former dry distillation gas composition
2the percentage by volume of gas, V%;
R---the hydrogen-carbon ratio of mending the clean dry distillation gas after carbon is 0.5 ~ 3.3;
The CO that α---carbonate decomposition generates
2gas reforming is the conversion ratio of CO gas;
For high temperature carbonization α=0.50 ~ 0.60, and medium temperature carbonization α=0.40 ~ 0.50.
Described carbonate benefit carbon raw material is the one in Wingdale, rhombspar and spathic iron ore.
Negatively charged ion in described Wingdale, rhombspar, spathic iron ore and magnesite is [CO
3]
2-, positively charged ion is Ca
2+, Mg
2+or Fe
2+.
The metal oxide content of described solid cleaning fuel is 0.3 ~ 20wt%; Quality index is: FC
d>=65%, V
adf≤ 6%, A
d≤ 35%, S
t,d< 1.0%.
The main component of the clean dry distillation gas after described benefit carbon is H
2, CO, CO
2and CH
4, surplus is N
2, C
mh
nand O
2.
Tar≤the 0.02g/m of the clean dry distillation gas after described benefit carbon
3, H
2s≤0.2g/m
3, NH
3≤ 0.05g/m
3, benzene≤4g/m
3.
Above-mentioned provided a kind of for the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio of the present invention is provided, compared with prior art, advantage that is that it directly brings and that certainly lead to and positively effect as follows:
In the methods of the invention, the benefit carbon desired raw material adopted is carbonate mineral, raw material sources extensively enrich, cheap, are added directly in as-fired coal, realize mending carbon by retort process, eliminate and build gas furnace and relevant purification, oxygen and equipment for purifying, simplify technological process, facility investment is low, comprehensive cost reduces more than 30%, can be widely used in the comprehensive utilization project of height, medium temperature carbonization coal gas.
In the methods of the invention, the metal oxide of carbonate decomposition by-product enters in produced solid cleaning fuel, in follow-up direct combustion processes, effectively controls SO
2discharge, create a further reduction the pollution of environment.
In the methods of the invention, the solid cleaning fuel containing metal oxide in combustion with SO
2generate the vitriol product of more difficult decomposition, vitriol is together discharged with lime-ash, thus reaches control SO
2the object of gaseous emission, its sulfur-fixing rate can reach more than 40%, effectively controls the pollution of environment.
In the methods of the invention, the gas of production, solid, liquid body product are clean fuel, compared with direct burning coal, contaminant reducing discharge more than 90%, to solution surrounding city life in the countryside coal, improve rural area and city environmental quality, reduce haze weather and be of great immediate significance.
In the methods of the invention, directly the burn amount of institute's pollution discharging thing of coal depends mainly on the height of volatile matter, and solid cleaning fuel volatile content is less than 6%; Gas products is as SNG, and liquid product is as LNG, methyl alcohol and synthetic oil, and its synthetic gas is all through the deep purifying of multiple operation, and foreign matter content is ppm(1,000,000/) level.Therefore, product is clean fuel.
Accompanying drawing explanation
Fig. 1 is the schema of the inventive method.
embodiment
below the specific embodiment of the present invention is made and illustrating further.
The present invention be directed to the carbonate mineral that China's natural endowment is abundant, and carbonate mineral is directly added in destructive distillation as-fired coal, in retort process, be decomposed into metal oxide and CO
2gas, part CO
2gas and pyrocarbon react and are converted into CO gas, CO
2dry distillation gas is entered, with the H of surplus with CO gas
2gas mates, and meets the hydrogen-carbon ratio requirement of synthetic gas; Meanwhile, the metal oxide of carbonate decomposition by-product enters in produced solid cleaning fuel, can in follow-up direct combustion processes control SO effectively
2discharge.
Its dry distillation gas comprises: high temperature carbonization coal gas, medium temperature carbonization coal gas.
It mends carbon method: gas retort as-fired coal material adds carbonate material, and main negatively charged ion is [CO
3]
2-, main positively charged ion is Ca
2+, Mg
2+, Fe
2+, as Wingdale (CaCO
3), rhombspar (CaCO
3mgCO
3), spathic iron ore (FeCO
3), magnesite (MgCO
3) etc.
It mends carbon principle: CaCO
3=CaO+CO
2
CaCO
3·MgCO
3= CaCO
3+ MgO + CO
2
3FeCO
3= Fe
3O
4+ 2CO
2+ CO
MgCO
3= MgO + CO
2
CO
2+ C = 2CO
Above-mentioned provided a kind of for the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio of the present invention, first the carbonate of drying is mended carbon raw material through slightly breaking, after dry grinding, add in destructive distillation as-fired coal in proportion, load in the lump in gas retort after mixing, through the CO that heating destructive distillation generates
2directly enter in dry distillation gas with CO gas, thus realize the object of mending carbon.Its concrete grammar follows these steps to carry out:
(1) determine that as-fired coal meets the requirements, quality index is: FC
d>=50%, V
adf>=25%, A
d≤ 25%, S
t,d< 1.5%;
(2) determine the burn out rate of carbonate benefit carbon raw material, the factor of created gase of as-fired coal and the composition of former dry distillation gas;
(3) the carbonate of drying is mended carbon raw material through thick broken, dry grinding, make powder particle size≤80 order;
(4) ground carbonate benefit carbon raw material is added in as-fired coal material and mixes, obtain mixture charge, mixture charge is loaded gas retort; For medium temperature carbonization, it is 0.5 ~ 28wt% of furnace coal weight that carbonate mends carbon raw material add-on, and high temperature carbonization, it is 4 ~ 30wt% of furnace coal weight that carbonate mends carbon raw material add-on;
(5) the mixture charge in gas retort is completely cut off air to heat, for medium temperature carbonization continuous heating 6 ~ 12h, furnace charge core temperature rises to 700 ~ 900 DEG C gradually; High temperature carbonization is continuous heating 12 ~ 24h then, and furnace charge core temperature rises to 900 ~ 1100 DEG C gradually; Then be down to normal temperature through quenching operation after being come out of the stove by the furnace charge of red heat, then after screening, be qualified solid cleaning fuel;
(6) the waste dry distillation gas that overflows of gas retort heat-processed, through tar removing, wet desulphurization, wash ammonia, wash the recovery of chemical products operations such as benzene after, tar≤0.02g/m
3, H
2s≤0.2g/m
3, NH
3≤ 0.05g/m
3, benzene≤4g/m
3, be the clean dry distillation gas after mending carbon;
(7) the carbon of dry distillation gas is supplemented, and the hydrogen-carbon ratio of mending the clean dry distillation gas after carbon is: R=(H
2-CO
2)/(CO+CO
2)=0.5 ~ 3.3, meets the benefit carbon requirement of synthetic gas.
The present invention, in above-mentioned implementation method, mends carbon material carbon hydrochlorate, includes but not limited to that negatively charged ion is [CO
3]
2-, include but not limited to that positively charged ion is Ca
2+, Mg
2+, Fe
2+, as Wingdale (CaCO
3), rhombspar (CaCO
3mgCO
3), spathic iron ore (FeCO
3), magnesite (MgCO
3) etc.
The present invention is in above-mentioned implementation method, it is form according to the coal gas of the factor of created gase of carbonate benefit carbon raw material burn out rate, as-fired coal material and the former destructive distillation before adding carbonate benefit carbon raw material that carbonate mends the carbon raw material add-on be added in as-fired coal, determines according to calculation formula; Before calculating carbonate benefit carbon raw material add-on, carbonate benefit carbon raw material burn out rate, as-fired coal factor of created gase and the former dry distillation gas composition before adding carbonate benefit carbon raw material can recording with the small coke oven test (as 40kg small coke oven) under gas retort same process condition according to as-fired coal in advance.
Calculation formula is as follows:
Wherein: M
s---carbonate mends the burn out rate of carbon raw material, wt%;
V
r---dry as-fired coal factor of created gase, Nm
3/ t;
V
cO---the percentage by volume of CO gas in former dry distillation gas composition, V%;
V
cO2---CO in former dry distillation gas composition
2the percentage by volume of gas, V%;
V
h2---H in former dry distillation gas composition
2the percentage by volume of gas, V%;
R---mend the hydrogen-carbon ratio of the clean dry distillation gas after carbon, be generally 0.5 ~ 3.3;
The CO that α---carbonate decomposition generates
2gas reforming is the conversion ratio of CO gas;
For high temperature carbonization α=0.50 ~ 0.60, and medium temperature carbonization α=0.40 ~ 0.50.
State on the invention in implementation method, as-fired coal is mixed coal, and high temperature carbonization is suitable for coal and comprises brown coal, hard coal and all bituminous coal; Medium temperature carbonization generally adopts other all coal except the main coking coals such as bottle coal, rich coal, coking coal, lean coal, as long-flame coal, non-caking coal, weakly caking coal, meager coal etc.
State on the invention in implementation method, mixture charge load the mode of gas retort by making side dress (abbreviation is made firm by ramming) firm by ramming, non-two kinds, top dress (be called for short top dress) modes of making firm by ramming load gas retort; Make firm by ramming and require as-fired coal index: fineness (≤3mm) >=85%, adhesive index=35 ~ 65; Top reload request as-fired coal index: fineness (≤3mm)=73 ± 2%, adhesive index >=65.
State on the invention in implementation method, dry distillation gas comprises high temperature carbonization (coke oven) coal gas, medium temperature carbonization coal gas.
State on the invention in implementation method, solid cleaning fuel is the solid product of coal destructive distillation, and its metal oxide content is 0.3 ~ 20wt%; Quality index is: FC
d>=65%, V
adf≤ 6%, A
d≤ 35%, S
t,d< 1.0%.
State on the invention in implementation method, spathic iron ore (FeCO
3) after heating destructive distillation, its degradation production Fe
3o
4enter solid cleaning fuel, add the iron level in this solid fuel ash content, as be conducive to improving pig iron output for blast furnace ironmaking.
State on the invention in implementation method, the method that recovery of chemical products operation adopts current dry distillation gas general: tar removing adopts electrical tar precipitator; Desulfurization (wet method) adopts modified ADA method, PDS+ tannin process or HPF method etc.; Wash ammonia and adopt sulfuric acid absorption method; Wash benzene and adopt washing oil absorption process.
State on the invention in implementation method, synthetic gas mainly methanation, synthesizing methanol and synthetic oil and all in building-up reactions with H
2, CO and CO
2gas is the unstripped gas of building-up reactions effective constituent.
Below by specific embodiment, the specific embodiment of the present invention is further detailed.
Embodiment 1
Limestone mine composition (wt%) is: CaO 54.3%, burn out rate 42.7%, impurity 3.0%.
As-fired coal material by 30% lean coal, 1/3 coking coal of 35%, the rich coal of 20% and 15% coking coal coordinate form; Its quality index (wt%): V
adf30.0%, A
d13.5%, FC
d60.6%, S
t,d0.67%, adhesive index=74, fineness (≤3mm)=73.6%.
As-fired coal material records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 24h, and furnace charge core temperature is come out of the stove after reaching 1100 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 353.4 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
260.1%, CH
422.8%, CO6.8%, CO
22.3%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.60, hydrogen-carbon ratio by 3.06, is then mended carbon raw material add-on calculation formula according to above-mentioned carbonate and is calculated the 9.2wt% that limestone mine add-on is furnace coal weight.
By the limestone mine of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 9.2wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 24h, after furnace charge core temperature reaches 1100 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
In solid cleaning fuel, CaO content is 6.2wt%, FC
d75.0%, V
adf1.2%, A
d24.1%, S
t,d0.59%;
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of HPF method, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.018g/m
3, H
2s 0.14g/m
3, NH
30.043g/m
3, benzene 3.8g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 55.1 | 20.9 | 4.9 | 12.5 | 4.2 | 1.9 | 0.5 | 3822.7 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=
3.03 ~ 3.09, mean value is 3.06, meets the benefit carbon requirement of methanation.
Embodiment 2
The composition (wt%) of dolomite mineral is: CaO 30.4%, MgO 21.7%, burn out rate 47.4%, impurity 0.46%.
As-fired coal by 30% lean coal, 1/3 coking coal of 35%, the rich coal of 20% and 15% coking coal coordinate form; Its quality index (wt%): V
adf30.0%, A
d13.5%, FC
d60.6%, S
t,d0.67%, adhesive index=74, fineness (≤3mm)=73.6%.
As-fired coal records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 20h, and furnace charge core temperature is come out of the stove after reaching 1050 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 353.4 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
257.5%, CH
424.5%, CO7.5%, CO
22.8%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.55, hydrogen-carbon ratio is by 3.20, then mending the known dolomite mineral add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 5.86wt% of furnace coal weight.
By the dolomite mineral of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 5.86wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 20h, after furnace charge core temperature reaches 1050 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
In solid cleaning fuel, CaO and content of MgO are 3.9wt%, FC
d77.2%, V
adf1.2%, A
d21.9%, S
t,d0.60%.
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of PDS+ tannin process, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.017g/m
3, H
2s 0.16g/m
3, NH
30.047g/m
3, benzene 3.7g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 54.1 | 23.1 | 4.7 | 11.2 | 4.3 | 2.1 | 0.5 | 3962.9 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=
3.17 ~ 3.23, mean value is 3.20, meets the benefit carbon requirement of methanation.
Embodiment 3
Spathic iron ore composition (wt%): FeO 52.7%, burn out rate 26.3%, impurity 21.0%.
As-fired coal by 30% lean coal, 1/3 coking coal of 35%, the rich coal of 20% and 15% coking coal coordinate form; Its quality index (wt%): V
adf30.0%, A
d13.5%, FC
d60.6%, S
t,d0.67%, adhesive index=74, fineness (≤3mm)=73.6%.
As-fired coal records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 15h, and furnace charge core temperature is come out of the stove after reaching 950 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 353.4 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
254.5%, CH
425.5%, CO10.7%, CO
23.7%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.55, hydrogen-carbon ratio is by 3.10, then mending the known spathic iron ore add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 4.3wt% of furnace coal weight.
By the spathic iron ore of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 4.3wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 15h, after furnace charge core temperature reaches 950 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
Fe in solid cleaning fuel
3o
4content is 2.9wt%, FC
d77.2%, V
adf1.2%, A
d21.9%, S
t,d0.60%.
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of modified ADA method, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.019g/m
3, H
2s 0.18g/m
3, NH
30.045g/m
3, benzene 3.9g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 53.6 | 25.1 | 3.9 | 11.6 | 4.3 | 1.3 | 0.2 | 4032.6 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=3.07 ~ 3.13, mean value is 3.10, meets the benefit carbon requirement of methanation.
Embodiment 4
Limestone mine composition (wt%): CaO 54.3%, burn out rate 42.7%, impurity 3.0%.
As-fired coal by 30% weakly caking coal, the long-flame coal of 40%, the gas-fat coal of 20% and 10% non-caking coal coordinate form; Its quality index (wt%): V
adf35.0%, A
d13.5%, FC
d56.2%, S
t,d0.84%, adhesive index=40, fineness (≤3mm)=86.5%.
As-fired coal records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 12h, and furnace charge core temperature is come out of the stove after reaching 900 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 305.3 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
253.2%, CH
426.5%, CO9.2%, CO
23.6%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.45, hydrogen-carbon ratio is by 3.07, then mending the known limestone mine add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 2.9wt% of furnace coal weight.
By the limestone mine of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 2.9wt% of furnace coal weight, mix the rear employing mode of making firm by ramming and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 12h, after furnace charge core temperature reaches 900 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
In solid cleaning fuel, CaO content is 2.1wt%, FC
d77.1%, V
adf3.3%, A
d20.5%, S
t,d0.80%.
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of HPF method, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.02g/m
3, H
2s 0.17g/m
3, NH
30.044g/m
3, benzene 4.0g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 51.7 | 25.7 | 3.9 | 10.7 | 4.6 | 2.9 | 0.5 | 4215.5 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=3.04 ~ 3.10, mean value is 3.07, meets the benefit carbon requirement of methanation.
Embodiment 5
Dolomite mineral composition (wt%): CaO 30.4%, MgO 21.7%, burn out rate 47.4%, impurity 0.46%.
As-fired coal by 30% weakly caking coal, the long-flame coal of 40%, the gas-fat coal of 20% and 10% non-caking coal coordinate form; Its quality index (wt%): V
adf35.0%, A
d13.5%, FC
d56.2%, S
t,d0.84%, adhesive index=40, fineness (≤3mm)=86.5%.
As-fired coal records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 10h, and furnace charge core temperature is come out of the stove after reaching 800 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 297.7 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
250.0%, CH
430.4%, CO8.2%, CO
24.0%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.45, hydrogen-carbon ratio is by 3.10, then mending the known dolomite mineral add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 2.0wt% of furnace coal weight.
By the dolomite mineral of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 2.0wt% of furnace coal weight, mix the rear employing mode of making firm by ramming and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 10h, after furnace charge core temperature reaches 800 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
In solid cleaning fuel, CaO and content of MgO are 1.4wt%, FC
d77.5%, V
adf3.8%, A
d19.8%, S
t,d0.8%.
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of PDS+ tannin process, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.016g/m
3, H
2s 0.19g/m
3, NH
30.048g/m
3, benzene 3.5g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 48.9 | 29.7 | 3.7 | 9.4 | 4.8 | 3.1 | 0.4 | 4470.2 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=3.07 ~ 3.13, mean value is 3.10, meets the benefit carbon requirement of methanation.
Embodiment 6
Spathic iron ore composition (wt%): FeO 52.7%, burn out rate 26.3%, impurity 21.0%.
As-fired coal by 30% weakly caking coal, the long-flame coal of 40%, the gas-fat coal of 20% and 10% non-caking coal coordinate form; Its quality index (wt%): V
adf35.0%, A
d13.5%, FC
d56.2%, S
t,d0.84%, adhesive index=40, fineness (≤3mm)=86.5%.
As-fired coal records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 6h, and furnace charge core temperature is come out of the stove after reaching 700 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 286.3 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
245.0%, CH
436.0%, CO6.7%, CO
25.0%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.45, hydrogen-carbon ratio is by 3.05, then mending the known spathic iron ore add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 2.5wt% of furnace coal weight.
By the spathic iron ore of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 2.5wt% of furnace coal weight, mix the rear employing mode of making firm by ramming and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 6h, after furnace charge core temperature reaches 700 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
Fe in solid cleaning fuel
3o
4content is 1.8wt%, FC
d76.4%, V
adf4.1%, A
d20.6%, S
t,d0.79%.
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of modified ADA method, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.018g/m
3, H
2s 0.17g/m
3, NH
30.046g/m
3, benzene 3.7g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 44.4 | 35.6 | 3.4 | 7.3 | 5.5 | 3.5 | 0.3 | 4835.2 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=3.02 ~ 3.08, mean value is 3.05, meets the benefit carbon requirement of methanation.
Embodiment 7
Limestone mine composition (wt%): CaO 54.3%, burn out rate 42.7%, impurity 3.0%.
As-fired coal by 30% lean coal, 1/3 coking coal of 35%, the rich coal of 20% and 15% coking coal coordinate form; Its quality index (wt%): V
adf30.0%, A
d13.5%, FC
d60.6%, S
t,d0.67%, adhesive index=74, fineness (≤3mm)=73.6%.
As-fired coal records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 20h, and furnace charge core temperature is come out of the stove after reaching 1050 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 353.4 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
257.5%, CH
424.5%, CO7.5%, CO
22.8%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.55, hydrogen-carbon ratio is by 2.12, then mending the known limestone mine add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 14.3wt% of furnace coal weight.
By the limestone mine of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 14.3wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 20h, after furnace charge core temperature reaches 1050 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
In solid cleaning fuel, CaO content is 9.3wt%, FC
d72.3%, V
adf1.2%, A
d26.8%, S
t,d0.57%;
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of PDS+ tannin process, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.017g/m
3, H
2s 0.16g/m
3, NH
30.047g/m
3, benzene 3.6g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 50.6 | 21.6 | 4.5 | 15.1 | 5.9 | 1.9 | 0.4 | 3844.0 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=2.09 ~ 2.15, mean value is 2.12, meets the benefit carbon requirement of methyl methanol syngas.
Embodiment 8
Dolomite mineral composition (wt%): CaO 30.4%, MgO 21.7%, burn out rate 47.4%, impurity 0.46%.
As-fired coal by 30% weakly caking coal, the long-flame coal of 40%, the gas-fat coal of 20% and 10% non-caking coal coordinate form; Its quality index (wt%): V
adf35.0%, A
d13.5%, FC
d56.2%, S
t,d0.84%, adhesive index=40, fineness (≤3mm)=86.5%.
As-fired coal records through 40kg small coke oven test (furnace charge completely cuts off air continuous heating 12h, and furnace charge core temperature is come out of the stove after reaching 900 DEG C, is down to normal temperature through quenching): as-fired coal factor of created gase is 282.7 Nm
3/ t; Adding carbonate to mend before carbon raw material in dry distillation gas: H
253.2%, CH
426.5%, CO9.2%, CO
23.6%, all the other are N
2, C
mh
n, O
2deng.CO
2transform ratio by 0.45, hydrogen-carbon ratio is by 1.20, then mending the known dolomite mineral add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 17.4wt% of furnace coal weight.
By the dolomite mineral of drying through thick broken, dry grinding, make powder particle size≤80 order; Be added in as-fired coal by the 17.4wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air continuous heating 12h, after furnace charge core temperature reaches 900 DEG C, after being come out of the stove by the furnace charge of red heat, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening.
In solid cleaning fuel, CaO and content of MgO are 10.6wt%, FC
d69.9%, V
adf3.2%, A
d27.6%, S
t,d0.56%.
The waste dry distillation gas that gas retort heat-processed is overflowed, washes ammonia through electrical tar precipitator tar removing, the wet desulphurization of HPF method, sulfuric acid absorption method, after washing oil absorption process washes the recovery of chemical products operations such as benzene, tar 0.019g/m
3, H
2s 0.18g/m
3, NH
30.045g/m
3, benzene 3.9g/m
3, be the clean dry distillation gas after mending carbon.
Its clean dry distillation gas composition mended after carbon is as follows:
| Component | H 2 | CH 4 | N 2 | CO | CO 2 | C mH n | O 2 | Thermal value kcal/Nm 3 |
| V% | 43.2 | 21.5 | 3.3 | 20.8 | 8.4 | 2.4 | 0.4 | 3883.7 |
In gained dry distillation gas, carbon is supplemented, actual hydrogen carbon ratio R=(H
2-CO
2)/(CO+CO
2)=1.17 ~ 1.23, H
2/ CO=2.05 ~ 2.11, mean value is 2.08, meets the benefit carbon requirement of synthetic oil synthetic gas.
Claims (7)
1., for the method for coal gas retort from main regulation dry distillation gas hydrogen-carbon ratio, method described in it follows these steps to carry out:
(1) determine that the quality index of as-fired coal is: FC
d>=50%, V
adf>=25%, A
d≤ 25%, S
t,d< 1.5%;
(2) determine the burn out rate of carbonate benefit carbon raw material, the factor of created gase of as-fired coal and the composition of former dry distillation gas;
(3) dried carbonate is mended carbon raw material through thick broken, dry grinding, make powder particle size≤80 order;
(4) ground carbonate benefit carbon raw material is added in as-fired coal and mixes, obtain mixture charge, mixture charge is loaded gas retort;
Medium temperature carbonization, it is 0.5 ~ 28wt% of furnace coal weight that carbonate mends carbon raw material add-on; Or
High temperature carbonization, it is 4 ~ 30wt% of furnace coal weight that carbonate mends carbon raw material add-on;
(5) the mixture charge in gas retort is completely cut off air heating, carry out benefit carbon by thermolysis;
Medium temperature carbonization continuous heating 6 ~ 12h, furnace charge core temperature rises to 700 ~ 900 DEG C gradually; Or
High temperature carbonization continuous heating 12 ~ 24h, furnace charge core temperature rises to 900 ~ 1100 DEG C gradually;
Then be down to normal temperature through quenching operation after being come out of the stove by red heat furnace charge, then through screening, namely obtain solid cleaning fuel;
(6) the waste dry distillation gas that overflows of gas retort heat-processed, through tar removing, wet desulphurization, wash ammonia, wash the recovery of chemical products operation of benzene after, be the clean dry distillation gas after mending carbon;
The hydrogen-carbon ratio of the clean dry distillation gas after gained mends carbon is: R=(H
2-CO
2)/(CO+CO
2)=0.5 ~ 3.3.
2. the method for claim 1, carbonate described in it mends the add-on of carbon raw material by following formulae discovery:
Wherein: M
s---the burn out rate of carbonate, wt%;
V
r---dry as-fired coal factor of created gase, Nm
3/ t;
V
cO---the percentage by volume of CO gas in former dry distillation gas composition, V%;
V
cO2---CO in former dry distillation gas composition
2the percentage by volume of gas, V%;
V
h2---H in former dry distillation gas composition
2the percentage by volume of gas, V%;
R---the hydrogen-carbon ratio of mending the clean dry distillation gas after carbon is 0.5 ~ 3.3;
The CO that α---carbonate decomposition generates
2gas reforming is the conversion ratio of CO gas;
For high temperature carbonization α=0.50 ~ 0.60, and medium temperature carbonization α=0.40 ~ 0.50.
3. the method for claim 1, carbonate benefit carbon raw material described in it is the one in Wingdale, rhombspar and spathic iron ore.
4. method as claimed in claim 3, the negatively charged ion in Wingdale, rhombspar and spathic iron ore described in it is [CO
3]
2-, positively charged ion is Ca
2+, Mg
2+or Fe
2+.
5. the method for claim 1, described in it, the metal oxide content of solid cleaning fuel is 0.3 ~ 20wt%; Quality index is: FC
d>=65%, V
adf≤ 6%, A
d≤ 35%, S
t,d< 1.0%.
6. the method for claim 1, the main component of mending the clean dry distillation gas after carbon described in it is H
2, CO, CO
2and CH
4, surplus is N
2, C
mh
nand O
2.
7. the method for claim 1, mends the tar≤0.02g/m of the clean dry distillation gas after carbon described in it
3, H
2s≤0.2g/m
3, NH
3≤ 0.05g/m
3, benzene≤4g/m
3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385983A (en) * | 1981-08-10 | 1983-05-31 | Chevron Research Company | Process for retorting oil shale mixtures with added carbonaceous material |
| CN101597527A (en) * | 2009-07-07 | 2009-12-09 | 山西科灵环境工程设计技术有限公司 | A kind of method of utilizing coke(oven)gas to produce synthetic natural gas |
| CN101955784A (en) * | 2010-09-27 | 2011-01-26 | 山东科技大学 | Coking composite leaning agent and preparation method thereof |
| CN103497840A (en) * | 2013-10-09 | 2014-01-08 | 太原理工大学 | Method for comprehensively utilizing abandoned oil in coking industries |
-
2014
- 2014-04-09 CN CN201410138709.8A patent/CN103937520B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4385983A (en) * | 1981-08-10 | 1983-05-31 | Chevron Research Company | Process for retorting oil shale mixtures with added carbonaceous material |
| CN101597527A (en) * | 2009-07-07 | 2009-12-09 | 山西科灵环境工程设计技术有限公司 | A kind of method of utilizing coke(oven)gas to produce synthetic natural gas |
| CN101955784A (en) * | 2010-09-27 | 2011-01-26 | 山东科技大学 | Coking composite leaning agent and preparation method thereof |
| CN103497840A (en) * | 2013-10-09 | 2014-01-08 | 太原理工大学 | Method for comprehensively utilizing abandoned oil in coking industries |
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