CN103881747B - Be that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas - Google Patents
Be that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas Download PDFInfo
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Abstract
A kind of is that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas, method described in it granularity≤80 object carbonate is mended carbon raw material to be added to loading gas retort heating after mixing in as-fired coal in proportion, then normal temperature is down to through quenching, again after screening, be solid cleaning fuel, the CO of generation
2directly enter in dry distillation gas with CO gas, with the H of surplus
2gas mates, and realizes the object of mending carbon.Carbonate mineral directly adds in destructive distillation as-fired coal by the present invention, utilizes the CO that its thermolysis produces
2with CO gas be dry distillation gas mend carbon.There is abundant raw material source, technological process be simple, low equipment investment, benefit carbon cost are low, the feature such as good economy performance, the comprehensive utilization project of height, medium temperature carbonization coal gas can be widely used in.
Description
Technical field
The present invention relates to a kind of method of producing synthetic oil, especially a kind of is that raw material produces synthetic oil by autonomous method of mending carbon with dry distillation gas.
Background technology
Synthetic oil is clean, the efficient liquid fuel with high added value produced by F-T synthesis technology, is the excellent substitute of petroleum products.The most important advantage of synthetic oil is the not undesirable components such as sulfur-bearing, nitrogen, nickel impurity and aromatic hydrocarbons, belongs to clean fuel, meets the strict demand of Modern Engine and day by day harsh environmental legislation completely.By F-T technique, dry distillation gas being changed into synthetic oil, opening a new way for producing clean fuel, to alleviation national oil intake pressure, ensure that energy security has important strategic importance.
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 producing synthetic oil through operations such as deep purifying, alkane transformations, decarburization, F-T synthesis, oil purificatioies, 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 oil synthetic gas.Existing high temperature carbonization technology such as metallurgical coke is produced, H in its dry distillation gas
2content reaches more than 50%, carbon content about 10%, and hydrogen-carbon ratio is up to more than 5; Existing medium temperature carbonization technology such as blue charcoal (middle temperature) 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 mended carbon to dry distillation gas.Carbon is mended in usual employing gasification of coal, for reducing the nitrogen content in synthetic oil synthetic gas, needs 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 prior art processes is complicated, and one-time investment is very large, more difficult at China's dry distillation of coal business enterprise expand.
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, by thermolysis, benefit carbon is carried out to synthetic oil synthetic gas, its objective is provide that a kind of technique is simple, less investment and cost low be that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas.
Object of the present invention is achieved by the following technical programs.
Be that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas, 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) 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 and mixes, and obtains mixture charge, mixture charge is loaded gas retort;
Medium temperature carbonization, it is 8 ~ 28wt% of furnace coal weight that carbonate mends carbon raw material add-on;
High temperature carbonization, carbonate mends 10 ~ 30wt% that carbon raw material add-on is then furnace coal weight;
(5) the mixture charge in gas retort is completely cut off air heating, by thermolysis and superfluous H
2gas coupling carries out benefit carbon;
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 be solid cleaning fuel after screening;
(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 tar≤0.02g/m
3, H
2s≤0.2g/m
3, NH
3≤ 0.05g/m
3, benzene≤4g/m
3;
(7) mend the clean dry distillation gas after carbon again through pre-treatment, for the first time organic sulfur conversion, thick desulfurization, second time organic sulfur conversion and fine de-sulfur even depth cleaning section, total sulfur≤0.1ppm;
(8) through alkane transformations, decarbonization process, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), and remove CO
2, make CH
4≤ 0.4%, CO
2≤ 0.1%;
(9) the hydrogen-carbon ratio of gained gaseous carbon element is r=H
2/ CO=1.80 ~ 2.15, are synthetic oil synthetic gas;
(10) synthetic oil synthetic gas is through F-T synthesis procedure, 190 ~ 270 DEG C, under 1.0 ~ 4.5MPa and catalysts conditions, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product based on diesel oil, wherein, diesel oil accounts for 70%, and all the other are LPG and petroleum naphtha.
In the technical scheme that the present invention is above-mentioned provided, 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 synthetic gas before alkane transformations, is generally 0.5 ~ 2.0;
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.
In the technical scheme that the present invention is above-mentioned provided, described carbonate benefit carbon raw material is the one in Wingdale, rhombspar, spathic iron ore and magnesite; 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+; In described solid cleaning fuel, metal oxide content is 5 ~ 20wt%; Quality index is: FC
d>=65%, V
adf≤ 6%, A
d≤ 35%, S
t,d< 1.0%; The composition of described synthetic oil synthetic gas is H
2and CO, surplus is N
2, CH
4and CO
2; Described synthetic oil synthetic gas synthesizes the synthetic oil product that can obtain based on diesel oil through F-T, wherein diesel oil accounts for more than 70%, and all the other are LPG, petroleum naphtha.
Realize a kind of technical scheme taking dry distillation gas as raw material warp autonomous benefit carbon and produce the method for synthetic oil that the present invention is above-mentioned, solve concrete benefit carbon problem to be solved by this invention, compared with prior art, the advantage had and positively effect are:
The inventive method abundant raw material source, technological process are simple, facility investment is low, mend carbon comprehensive cost extremely low, can be widely used in the comprehensive utilization project of height, medium temperature carbonization coal gas.
It is the carbonate mineral that China's natural endowment is abundant that the inventive method mends carbon desired raw material, and source is wide, low price; Be 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, comprehensive cost reduces by more than 30%.
The metal oxide of the inventive method carbonate decomposition by-product enters in produced solid cleaning fuel, can in follow-up direct combustion processes effective control SO
2discharge.
The solid cleaning fuel that the inventive method contains 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 effect of discharge, sulfur-fixing rate can reach more than 40%.
The product that the inventive method is produced is clean fuel, and compared with direct burning coal, contaminant reducing discharge more than 90%, to solution surrounding city life in the countryside coal, improves rural area and city environmental quality, reduce haze weather and have significant role.
Directly the burn amount of institute's pollution discharging thing of the inventive method coal depends mainly on the height of volatile matter, and solid cleaning fuel volatile content is less than 6%; Liquid product synthetic oil, its synthetic gas is 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 that the present invention mends carbon method.
embodiment
Below the specific embodiment of the present invention is further illustrated.
A kind of method taking dry distillation gas as raw material warp autonomous benefit carbon and produce natural gas liquids that the present invention is above-mentioned provided, for the abundant carbonate mineral of China's natural endowment, it creatively directly adds in destructive distillation as-fired coal by the present invention, is decomposed into metal oxide and CO in retort process
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 oil synthetic gas; Meanwhile, the metal oxide of carbonate decomposition by-product enters in produced solid cleaning fuel, can in follow-up direct combustion processes effective control SO
2discharge.
Abundant raw material source of the present invention, technological process are simple, facility investment is low, mend carbon comprehensive cost extremely low, can be widely used in the comprehensive utilization project of height, medium temperature carbonization coal gas.Meanwhile, the solid cleaning fuel of by-product, due to containing a large amount of metal oxides, has effectively control SO
2effect of discharge, is very applicable to vast rural area and industrial and mining enterprises directly use.The product such as tar, crude benzol of recovery of chemical products is the industrial chemicals that added value is very high.
Dry distillation gas comprises: high temperature carbonization (coke oven) coal gas, medium temperature carbonization coal gas.
Mend carbon method: gas retort as-fired coal 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.
Mend 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
A kind of method taking dry distillation gas as raw material warp autonomous benefit carbon and produce synthetic oil provided by the present invention, first the carbonate of drying is mended carbon raw material through slightly breaking, after dry grinding, add in proportion in destructive distillation as-fired coal, after mixing, load gas retort in the lump, 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 and mixes, and obtains mixture charge, mixture charge is loaded gas retort; For medium temperature carbonization, it is 8 ~ 28wt% of furnace coal weight that carbonate mends carbon raw material add-on, and high temperature carbonization, carbonate mends 10 ~ 30wt% that carbon raw material add-on is then furnace coal weight;
(5) the mixture charge in gas retort is completely cut off air heating, 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 be qualified solid cleaning fuel after screening;
(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, guarantee 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) mend the clean dry distillation gas after carbon again through pre-treatment, for the first time organic sulfur conversion, thick desulfurization, second time organic sulfur conversion and fine de-sulfur even depth cleaning section, total sulfur≤0.1ppm;
(8) through alkane transformations, decarbonization process, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), and remove CO
2, guarantee CH
4≤ 0.4%, CO
2≤ 0.1%;
(9) gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transformations
2/ CO=1.80 ~ 2.15, meet the benefit carbon requirement of synthetic oil synthesis, are qualified synthetic oil synthetic gas.
(10) synthetic oil synthetic gas is through F-T synthesis procedure, 190 ~ 270 DEG C, under 1.0 ~ 4.5MPa and catalysts conditions, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product (diesel oil accounts for more than 70%, and all the other are LPG, petroleum naphtha etc.) based on diesel oil.
Implement technique scheme, carbonate mends carbon raw material, 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.
Implement technique scheme, the add-on that carbonate mends carbon raw material mends carbon raw material burn out rate, as-fired coal factor of created gase according to carbonate and add carbonate to mend the former dry distillation gas composition before carbon raw material, 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---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 synthetic gas before alkane transformations, R=(H
2-CO
2)/(CO+CO
2)=0.5 ~ 2.0;
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.
In above-mentioned embodiment, 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.
In above-mentioned embodiment, destructive distillation as-fired coal fills (abbreviation is made firm by ramming) by making side firm by ramming, non-top dress (being called for short top to fill) two kinds of 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.
In above-mentioned embodiment, dry distillation gas, comprises high temperature carbonization (coke oven) coal gas, medium temperature carbonization coal gas.
In above-mentioned embodiment, solid cleaning fuel is the solid product of coal destructive distillation, and its metal oxide content is 5 ~ 20wt%, FC
d>=65%, V
adf≤ 6%, A
d≤ 35%, S
t,d< 1.0%.
In above-mentioned embodiment, 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.
In above-mentioned embodiment, deep purifying operation, wherein pre-treatment can adopt filtration or Temp .-changing adsorption (TSA); Thick desulfurization and fine de-sulfur adopt dry desulfurization; Organic sulfur conversion adopts hydrocracking or hydrolysis technology; The sweetening agent that described dry desulfurization uses comprise in ferric oxide, manganese oxide, zinc oxide or gac one or more; The catalyzer that described hydrocracking uses comprise in iron molybdenum, nickel molybdenum and cobalt molybdenum hydrogenation catalyst one or more; The catalyzer that described hydrolysis uses comprises normal temperature or the agent of middle temperature tempreture organic sulphur hydrolysis.
In above-mentioned embodiment, alkane transformations operation can adopt pure oxygen catalytic partial oxidation technique or Steam Reforming Process.
In above-mentioned embodiment, decarbonization process can adopt chemical absorption method, physical absorption method, mixed solvent absorption process and molecular sieve adsorption etc., and chemical absorption method can be divided into again hydramine method, alkaline salt solution method; Hydramine method is commonly used absorption agent and is comprised monoethanolamine (MEA), diethanolamine (DEA), diisopropanolamine (DIPA) (DIPA), methyldiethanolamine (MDEA) etc.
In above-mentioned embodiment, the catalyzer in F-T synthesis procedure generally adopts iron-based or cobalt-base catalyst, and reactor generally adopts fixed bed or paste state bed reactor.
Below by specific embodiment, the specific embodiment of the present invention is further detailed.
Embodiment 1
Implementing a kind of is that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas, and described in it, the concrete steps of method are as follows:
Raw material limestone ore deposit composition (wt%): CaO54.3%, burn out rate 42.7%, impurity 3.0%.
Raw material as-fired coal material composition (wt%): 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%.
Mend carbon method: as-fired coal 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 353.4Nm
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, before alkane transformations, hydrogen-carbon ratio R is by 1.35, then mending the known limestone mine add-on of carbon raw material add-on calculation formula by above-mentioned carbonate is the 29.0wt% 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 29.0wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air heating 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 17.4wt%, FC
d65.2%, V
adf1.1%, A
d34.0%, S
t,d0.54%.
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
2s0.14g/m
3, NH
30.043g/m
3, benzene 3.8g/m
3, be the clean dry distillation gas after mending carbon.
Mend the clean dry distillation gas after carbon again through TSA pre-treatment, one-level iron molybdenum hydrogenation organic sulfur conversion, coarse iron oxide desulfurization, secondary iron molybdenum hydrogenation organic sulfur conversion and middle temperature zinc oxide fine de-sulfur even depth cleaning section, total sulfur=0.084ppm; Then through alkane transformations operation, pure oxygen catalytic partial oxidation technique is adopted, under nickel catalyzator and 980 DEG C of conditions, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), CH in synthetic gas
4=0.4%; CO is removed finally by MDEA decarbonization process
2, CO
2=0.03%.Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transformations
2/ CO=2.0 ~ 2.06, mean value is 2.03, meets the benefit carbon requirement of synthetic oil synthesis, is qualified synthetic oil synthetic gas.
Its composition is as follows:
| Component | H 2 | CO | CH 4 | N 2 | Add up to |
| V% | 64.7 | 31.9 | 0.3 | 3.1 | 100.0 |
Synthetic oil synthetic gas is through F-T synthesis procedure, 230 DEG C, under the catalyst based condition of 3.0MPa and Fe, in paste state bed reactor, generate thick synthetic oil, then through oil purification operation, obtain the synthetic oil product (diesel oil accounts for 72%, and all the other are LPG, petroleum naphtha etc.) based on diesel oil.
Embodiment 2
Dolomite mineral composition (wt%): CaO30.4%, MgO21.7%, 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 353.4Nm
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, before alkane transformations, hydrogen-carbon ratio R is by 1.15, then mending the known dolomite mineral add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 28.0wt% 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 28.0wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air heating 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 16.5wt%, FC
d66.6%, V
adf1.1%, A
d32.5%, S
t,d0.54%.
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
2s0.16g/m
3, NH
30.047g/m
3, benzene 3.7g/m
3, be the clean dry distillation gas after mending carbon.
Mend the clean dry distillation gas after carbon again through TSA pre-treatment, one-level iron molybdenum hydrogenation organic sulfur conversion, coarse iron oxide desulfurization, secondary iron molybdenum hydrogenation organic sulfur conversion and middle temperature zinc oxide fine de-sulfur even depth cleaning section, total sulfur=0.078ppm; Then through alkane transformations operation, pure oxygen catalytic partial oxidation technique is adopted, under nickel catalyzator and 980 DEG C of conditions, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), CH in synthetic gas
4=0.4%; CO is removed finally by MDEA decarbonization process
2, CO
2=0.04%.
Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transformations
2/ CO=1.94 ~ 2.0, mean value is 1.97, meets the benefit carbon requirement of synthetic oil synthesis, is qualified synthetic oil synthetic gas.
Its composition is as follows:
| Component | H 2 | CO | CH 4 | N 2 | Add up to |
| V% | 64.2 | 32.6 | 0.4 | 2.8 | 100.0 |
Synthetic oil synthetic gas through F-T synthesis procedure, 240 DEG C, under the catalyst based condition of 3.0MPa and Fe, in paste state bed reactor, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product (diesel oil accounts for 73%, and all the other are LPG, petroleum naphtha etc.) based on diesel oil.
Embodiment 3
Dolomite mineral composition (wt%): CaO30.4%, MgO21.7%, 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 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 353.4Nm
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, before alkane transformations, hydrogen-carbon ratio R is by 1.35, then mending the known dolomite mineral add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 18.0wt% 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 18.0wt% of furnace coal weight, mix rear employing top dress mode and load gas retort; Mixture charge in gas retort is completely cut off air heating 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.
In solid cleaning fuel, CaO and content of MgO are 11.2wt%, FC
d71.1%, V
adf1.2%, A
d28.0%, 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 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
2s0.18g/m
3, NH
30.045g/m
3, benzene 3.9g/m
3, be the clean dry distillation gas after mending carbon.
Mend the clean dry distillation gas after carbon again through TSA pre-treatment, one-level iron molybdenum hydrogenation organic sulfur conversion, coarse iron oxide desulfurization, secondary iron molybdenum hydrogenation organic sulfur conversion and middle temperature zinc oxide fine de-sulfur even depth cleaning section, total sulfur=0.089ppm; Then through alkane transformations operation, pure oxygen catalytic partial oxidation technique is adopted, under nickel catalyzator and 980 DEG C of conditions, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), CH in synthetic gas
4=0.4%; CO is removed finally by MDEA decarbonization process
2, CO
2=0.02%.
Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transformations
2/ CO=2.06 ~ 2.12, mean value is 2.09, meets the benefit carbon requirement of synthetic oil synthesis, is qualified synthetic oil synthetic gas.
Its composition is as follows:
| Component | H 2 | CO | CH 4 | N 2 | Add up to |
| V% | 65.7 | 31.4 | 0.4 | 2.5 | 100.0 |
Synthetic oil synthetic gas through F-T synthesis procedure, 245 DEG C, under the catalyst based condition of 3.0MPa and Fe, in paste state bed reactor, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product (diesel oil accounts for 71%, and all the other are LPG, petroleum naphtha etc.) based on diesel oil.
Embodiment 4
Limestone mine composition (wt%): CaO54.3%, 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 305.3Nm
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, before alkane transformations, hydrogen-carbon ratio R is by 1.01, then mending the known limestone mine add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 25.6wt% 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 25.6wt% add-on 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 heating 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 16.2wt%, FC
d65.1%, V
adf2.8%, A
d32.8%, S
t,d0.71%.
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
2s0.17g/m
3, NH
30.044g/m
3, benzene 4.0g/m
3, be the clean dry distillation gas after mending carbon.
Mend the clean dry distillation gas after carbon again through TSA pre-treatment, medium temperature hydrolyzation organic sulfur conversion, coarse iron oxide desulfurization, one-level iron molybdenum hydrogenation organic sulfur conversion and active-carbon finely desulfurization even depth cleaning section, total sulfur=0.077ppm; Then through alkane transformations operation, pure oxygen catalytic partial oxidation technique is adopted, under nickel catalyzator and 980 DEG C of conditions, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), CH in synthetic gas
4=0.4%; CO is removed finally by MDEA decarbonization process
2, CO
2=0.03%.
Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transformations
2/ CO=1.95 ~ 2.01, mean value is 1.98, meets the benefit carbon requirement of synthetic oil synthesis, is qualified synthetic oil synthetic gas.
Its composition is as follows:
| Component | H 2 | CO | CH 4 | N 2 | Add up to |
| V% | 64.7 | 32.6 | 0.4 | 2.3 | 100.0 |
Synthetic oil synthetic gas through F-T synthesis procedure, 245 DEG C, under the catalyst based condition of 4.0MPa and Co, in paste state bed reactor, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product (diesel oil accounts for 74%, and all the other are LPG, petroleum naphtha etc.) based on diesel oil.
Embodiment 5
Dolomite mineral composition (wt%): CaO30.4%, MgO21.7%, 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 297.7Nm
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, before alkane transformations, hydrogen-carbon ratio R is by 0.87, then mending the known dolomite mineral add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 24.0wt% 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 24.0wt% 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 heating 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 14.9wt%, FC
d66.7%, V
adf2.9%, A
d31.2%, S
t,d0.72%.
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
2s0.19g/m
3, NH
30.048g/m
3, benzene 3.5g/m
3, be the clean dry distillation gas after mending carbon.
Mend the clean dry distillation gas after carbon again through TSA pre-treatment, medium temperature hydrolyzation organic sulfur conversion, coarse iron oxide desulfurization, one-level iron molybdenum hydrogenation organic sulfur conversion and active-carbon finely desulfurization even depth cleaning section, total sulfur=0.062ppm; Then through alkane transformations operation, pure oxygen catalytic partial oxidation technique is adopted, under nickel catalyzator and 980 DEG C of conditions, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), CH in synthetic gas
4=0.4%; CO is removed finally by MDEA decarbonization process
2, CO
2=0.04%.
Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transformations
2/ CO=1.90 ~ 1.96, mean value is 1.93, meets the benefit carbon requirement of synthetic oil synthesis, is qualified synthetic oil synthetic gas.
Its composition is as follows:
| Component | H 2 | CO | CH 4 | N 2 | Add up to |
| V% | 64.2 | 33.3 | 0.4 | 2.1 | 100.0 |
Synthetic oil synthetic gas through F-T synthesis procedure, 230 DEG C, under the catalyst based condition of 4.0MPa and Co, in paste state bed reactor, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product (diesel oil accounts for 73%, and all the other are LPG, petroleum naphtha etc.) based on diesel oil.
Embodiment 6
Dolomite mineral composition (wt%): CaO30.4%, MgO21.7%, 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 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 286.3Nm
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, before alkane transformations, hydrogen-carbon ratio R is by 0.84, then mending the known dolomite mineral add-on of carbon raw material add-on calculation formula according to above-mentioned carbonate is the 27.0wt% 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 27.0wt% 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 heating 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.
In solid cleaning fuel, CaO and content of MgO are 16.4wt%, FC
d65.1%, V
adf3.4%, A
d32.4%, S
t,d0.71%.
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
2s0.17g/m
3, NH
30.046g/m
3, benzene 3.7g/m
3, be the clean dry distillation gas after mending carbon.
Mend the clean dry distillation gas after carbon again through TSA pre-treatment, medium temperature hydrolyzation organic sulfur conversion, coarse iron oxide desulfurization, one-level iron molybdenum hydrogenation organic sulfur conversion and active-carbon finely desulfurization even depth cleaning section, total sulfur=0.069ppm; Then through alkane transformations operation, pure oxygen catalytic partial oxidation technique is adopted, under nickel catalyzator and 980 DEG C of conditions, by CH
4, C
mh
nbe converted into the active principle (H of synthetic gas
2+ CO), CH in synthetic gas
4=0.4%; CO is removed finally by MDEA decarbonization process
2, CO
2=0.03%.
Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transformations
2/ CO=1.93 ~ 2.0, mean value is 1.96, meets the benefit carbon requirement of synthetic oil synthesis, is qualified synthetic oil synthetic gas.
Its composition is as follows:
| Component | H 2 | CO | CH 4 | N 2 | Add up to |
| V% | 64.7 | 33.0 | 0.4 | 1.9 | 100.0 |
Synthetic oil synthetic gas through F-T synthesis procedure, 220 DEG C, under the catalyst based condition of 4.0MPa and Co, in paste state bed reactor, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product (diesel oil accounts for 71%, and all the other are LPG, petroleum naphtha etc.) based on diesel oil.
Claims (5)
1. be that raw material mends through autonomous the method that carbon produces synthetic oil with dry distillation gas, 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) 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 and mixes, and obtains mixture charge, mixture charge is loaded gas retort;
Medium temperature carbonization, it is 8 ~ 28wt% of furnace coal weight that carbonate mends carbon raw material add-on; Or
High temperature carbonization, carbonate mends 10 ~ 30wt% that carbon raw material add-on is then furnace coal weight;
(5) the mixture charge in gas retort is completely cut off air heating, by thermolysis and superfluous H
2gas coupling carries out benefit carbon;
Medium temperature carbonization continuous heating 6 ~ 12h, furnace charge core temperature rises to 700 ~ 900 DEG C gradually; Or
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 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 tar≤0.02g/m
3, H
2s≤0.2g/m
3, NH
3≤ 0.05g/m
3, benzene≤4g/m
3;
(7) mend the clean dry distillation gas after carbon again through the deep purifying operation of pre-treatment, for the first time organic sulfur conversion, thick desulfurization, for the second time organic sulfur conversion and fine de-sulfur, total sulfur≤0.1ppm;
(8) through alkane transformations, decarbonization process, by CH
4, C
mh
nbe converted into synthetic gas, its active principle is (H
2+ CO), and remove CO
2, make CH
4≤ 0.4%, CO
2≤ 0.1%;
(9) the hydrogen-carbon ratio of gained gaseous carbon element is r=H
2/ CO=1.80 ~ 2.15, are synthetic oil synthetic gas;
(10) synthetic oil synthetic gas is through F-T synthesis procedure, 190 ~ 270 DEG C, under 1.0 ~ 4.5MPa and catalysts conditions, generate thick synthetic oil; Again through oil purification operation, obtain the synthetic oil product based on diesel oil, wherein, diesel oil accounts for 70%, and all the other are LPG and petroleum naphtha;
Described burn out rate, the factor of created gase of as-fired coal and the composition of former dry distillation gas determining that carbonate mends carbon raw material is recording in advance with the small coke oven test under gas retort same process condition according to as-fired coal;
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 synthetic gas before alkane transformations, R=(H
2-CO
2)/(CO+CO
2)=0.5 ~ 2.0;
The CO that α---carbonate decomposition generates
2gas reforming is the conversion ratio of CO gas;
High temperature carbonization α=0.50 ~ 0.60; Medium temperature carbonization α=0.40 ~ 0.50.
2. the method for claim 1, carbonate benefit carbon raw material described in it is the one in Wingdale, rhombspar, spathic iron ore and magnesite.
3. method as claimed in claim 2, the ultimate particle in Wingdale, rhombspar, spathic iron ore and magnesite chemical constitution described in it: negatively charged ion is [CO
3]
2-, positively charged ion is Ca
2+, Mg
2+or Fe
2+.
4. the method for claim 1, in solid cleaning fuel described in it, metal oxide content is 5 ~ 20wt%; Quality index is: FC
d>=65%, V
adf≤ 6%, A
d≤ 35%, S
t,d< 1.0%.
5. the method for claim 1, described in it, the composition of synthetic oil synthetic gas is H
2and CO, surplus is N
2, CH
4and CO
2.
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