CN103881747A - Method for producing synthetic oil from dry distillation gas through autonomous carbon supplementing - Google Patents

Method for producing synthetic oil from dry distillation gas through autonomous carbon supplementing Download PDF

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CN103881747A
CN103881747A CN201410138724.2A CN201410138724A CN103881747A CN 103881747 A CN103881747 A CN 103881747A CN 201410138724 A CN201410138724 A CN 201410138724A CN 103881747 A CN103881747 A CN 103881747A
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gas
carbon
dry distillation
synthetic
coal
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CN201410138724.2A
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CN103881747B (en
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杜文广
刘守军
张智聪
上官炬
杨颂
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太原理工大学
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Abstract

The invention relates to a method for producing synthetic oil from dry distillation gas through autonomous carbon supplementing. The method comprises the steps of adding a carbonate carbon supplementing raw material, of which the granularity is not greater than 80 meshes, into furnace charging coal proportionally, mixing, then, loading the mixture to a dry distillation furnace for heating, then, quenching to cool to normal temperature, then, screening, so as to obtain solid clean fuel, and enabling produced CO2 and CO to directly enter the dry distillation gas, so as to be matched with superfluous H2, thereby realizing the aim of carbon supplementing. According to the method disclosed by the invention, a carbonate mineral is directly added into the dry-distillation furnace charging coal, and the CO2 and CO produced due to thermal decomposition are applied to the carbon supplementing of the dry distillation gas; the method has the characteristics of rich source of raw materials, simple process flow, small equipment investment, low carbon supplementing cost, good economical efficiency and the like, and can be widely applied to the project of comprehensive utilization of high and medium-temperature dry distillation gases.

Description

The method of producing synthetic oil through autonomous benefit carbon take dry distillation gas as raw material

Technical field

The present invention relates to a kind of method of producing synthetic oil, especially a kind of method production synthetic oil that passes through independently to mend carbon take dry distillation gas as raw material.

Background technology

Synthetic oil is clean, the efficient liquid fuel with high added value of producing by Fischer-Tropsch synthetic technology, is the good substitute of petroleum products.The most important advantage of synthetic oil is the undesirable components such as sulfur-bearing, nitrogen, nickel impurity and aromatic hydrocarbons not, 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 is changed into synthetic oil, opened up a new way for producing clean fuel, to alleviating national petroleum import pressure, ensureing that energy security has important strategic importance.

Coal burning be China at present and even from now on the long duration obtain the major way of the energy, the direct burning of a large amount of coals, 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 economy poor.Therefore implement destructive distillation (pulling out head) to using coal, fully reclaim contained chemical in coal, efficient cascade utilization coal in the field of business aspect 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, the operations such as, oil purification synthetic through deep purifying, alkane conversion, decarburization, F-T can be used for producing synthetic oil, thereby improve the added value of dry distillation gas, and 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 surplus, hydrogen-carbon ratio does not meet the mol ratio requirement of synthetic oil synthetic gas.Existing high temperature carbonization technology is produced as metallurgical coke, H in its dry distillation gas 2content reaches more than 50%, carbon content approximately 10%, and hydrogen-carbon ratio is up to more than 5; Existing medium temperature carbonization technology is as blue charcoal (middle temperature) production, H in its dry distillation gas 2content reaches more than 40%, and hydrogen-carbon ratio reaches more than 3.5.

Wish must be mended carbon to dry distillation gas by the exess of H2 gas complete reaction.Conventionally adopt gasification of coal to mend carbon, for reducing the nitrogen content in synthetic oil synthetic gas, need empty point pure oxygen processed as vaporized chemical.As existing fixed bed pure oxygen gasification is mended carbon technique, take coke or hard coal as 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 units, and need join larger air separation facility, and feed coal requires very high.

Above-mentioned prior art processes complexity, 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 mending carbon raw material, directly adding destructive distillation to enters in stove coal, by thermolysis, synthetic oil synthetic gas is mended to carbon, its objective is provide that a kind of technique is simple, less investment and cost low take dry distillation gas as raw material through the autonomous method of mending carbon and producing synthetic oil.

Object of the present invention is achieved by the following technical programs.

Take dry distillation gas as raw material, through an autonomous method of mending carbon production synthetic oil, described in it, method follows these steps to carry out:

(1) determine into the quality index of stove coal and be: FC d>=50%, V adf>=25%, A d≤ 25%, S t,d< 1.5%;

(2) determine that carbonate mends the burn out rate of carbon raw material, enters the factor of created gase of stove coal and the composition of former dry distillation gas;

(3) dry carbonate is mended to carbon raw material through thick broken, dry grinding, made breeze granularity≤80 order;

(4) ground carbonate benefit carbon raw material is added in stove coal and mixes, and obtains mixture charge, packs mixture charge into gas retort;

Medium temperature carbonization, carbonate is mended 8~28wt% that carbon raw material add-on is furnace coal weight;

High temperature carbonization, it is 10~30wt% of furnace coal weight that carbonate is mended carbon raw material add-on;

(5) by isolated the mixture charge in gas retort air heating, by thermolysis and superfluous H 2gas coupling is mended carbon;

Medium temperature carbonization continuous heating 6~12h, furnace charge core temperature rises to 700~900 ℃ gradually;

High temperature carbonization is continuous heating 12~24h, and furnace charge core temperature rises to 900~1100 ℃ gradually;

Then after the furnace charge of red heat being come out of the stove, be down to normal temperature through quenching operation, then be solid cleaning fuel after screening;

(6) the waste dry distillation gas that gas retort heat-processed is overflowed, through tar removing, wet desulphurization, wash ammonia, wash after the recovery of chemical products operation of benzene, is the clean dry distillation gas of mending after 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 clean dry distillation gas after carbon again through pre-treatment, organosulfur transforms for the first time, thick desulfurization, organosulfur transforms and smart desulfurization even depth cleaning section for the second time, total sulfur≤0.1ppm;

(8) through alkane conversion, 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, under 190~270 ℃, 1.0~4.5MPa and catalyzer condition, generates thick synthetic oil; Through oil purification operation, obtain take diesel oil as main synthetic oil product, wherein, diesel oil accounts for 70% again, and all the other are LPG and petroleum naphtha.

In above-mentioned the provided technical scheme of the present invention, described carbonate is mended the add-on of carbon raw material and is calculated by following formula:

Wherein: M s---the burn out rate of carbonate, wt%;

V r---dry enter stove 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%;

Before R---alkane transforms, the hydrogen-carbon ratio of synthetic gas, 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 above-mentioned the provided technical scheme of the present invention, it is the one in Wingdale, rhombspar, spathic iron ore and magnesite that described carbonate is mended carbon raw material; 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 is through the synthetic synthetic oil product that can obtain take diesel oil as master of F-T, and wherein diesel oil accounts for more than 70%, and all the other are LPG, petroleum naphtha.

Realize the above-mentioned a kind of technical scheme of producing the method for synthetic oil take dry distillation gas as raw material through autonomous benefit carbon of the present invention, solved concrete benefit carbon problem to be solved by this invention, compared with prior art, the advantage and the positively effect that have are:

The inventive method raw material sources are abundant, technological process is 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 is mended carbon desired raw material, and source is wide, low price; Be added directly in stove coal, realized and mended carbon by retort process, saved construction gas furnace and relevant purification, oxygen and equipment for purifying, simplified technological process, comprehensive cost reduces 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, effectively control SO 2discharge.

The solid cleaning fuel that the inventive method contains metal oxide in combustion processes with SO 2the vitriol product that generates more difficult decomposition, vitriol is together discharged with lime-ash, controls SO thereby reach 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 discharges more than 90%, to solving surrounding city life in the countryside coal, improves rural area and city environmental quality, reduces haze weather and has 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, solid cleaning fuel volatile content less than 6%; Liquid product synthetic oil, its synthetic gas is through the deep purifying of multiple operations, foreign matter content be 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 of producing natural gas liquids through autonomous benefit carbon take dry distillation gas as raw material that the present invention is above-mentioned provided, the carbonate mineral abundant for China's natural endowment, the present invention creatively directly adds it to destructive distillation and enters in stove coal, is decomposed into metal oxide and CO in retort process 2gas, part CO 2gas reacts with pyrocarbon and is converted into CO gas, CO 2enter dry distillation gas with CO gas, with superfluous H 2gas coupling, 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, effectively control SO 2discharge.

Raw material sources of the present invention are abundant, technological process is 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, owing to containing a large amount of metal oxides, has effective control SO 2effect of discharge is applicable to vast rural area and industrial and mining enterprises and directly uses very much.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 enters stove coal and 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 of producing synthetic oil through autonomous benefit carbon take dry distillation gas as raw material provided by the present invention, first dry carbonate to be mended to carbon raw material through slightly breaking, after dry grinding, add in proportion destructive distillation to enter in stove coal, after mixing, pack in the lump gas retort into, the CO generating through heating destructive distillation 2directly enter in dry distillation gas with CO gas, thereby realize the object of mending carbon.Its concrete grammar follows these steps to carry out:

(1) determine into stove coal and meet the requirements, quality index is: FC d>=50%, V adf>=25%, A d≤ 25%, S t,d< 1.5%;

(2) determine that carbonate mends the burn out rate of carbon raw material, enters the factor of created gase of stove coal and the composition of former dry distillation gas;

(3) dry carbonate is mended to carbon raw material through thick broken, dry grinding, made breeze granularity≤80 order;

(4) ground carbonate benefit carbon raw material is added in stove coal and mixes, and obtains mixture charge, packs mixture charge into gas retort; For medium temperature carbonization, carbonate is mended 8~28wt% that carbon raw material add-on is furnace coal weight, and high temperature carbonization, it is 10~30wt% of furnace coal weight that carbonate is mended carbon raw material add-on;

(5) the mixture charge in gas retort is completely cut off to air heating, medium temperature carbonization continuous heating 6~12h, furnace charge core temperature rises to 700~900 ℃ gradually; High temperature carbonization is continuous heating 12~24h, and furnace charge core temperature rises to 900~1100 ℃ gradually; Then after the furnace charge of red heat being come out of the stove, be down to normal temperature through quenching operation, then be qualified solid cleaning fuel after screening;

(6) the waste dry distillation gas that gas retort heat-processed is overflowed, through tar removing, wet desulphurization, wash ammonia, wash after the recovery of chemical products operations such as benzene, guarantees 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 of mending after carbon;

(7) mend clean dry distillation gas after carbon again through pre-treatment, organosulfur transforms for the first time, thick desulfurization, organosulfur transforms and smart desulfurization even depth cleaning section for the second time, total sulfur≤0.1ppm;

(8) through alkane conversion, 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 transforms 2/ CO=1.80~2.15, meet the synthetic benefit carbon requirement of synthetic oil, are qualified synthetic oil synthetic gas.

(10) synthetic oil synthetic gas is through F-T synthesis procedure, under 190~270 ℃, 1.0~4.5MPa and catalyzer condition, generates thick synthetic oil; Through oil purification operation, obtain take diesel oil as main synthetic oil product (diesel oil accounts for more than 70%, and all the other are LPG, petroleum naphtha etc.) again.

Implement technique scheme, carbonate is mended 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 is mended carbon raw material is to mend carbon raw material burn out rate, enter stove coal factor of created gase and add carbonate according to carbonate to mend the former dry distillation gas composition before carbon raw material, determines according to calculation formula; Calculate carbonate and mend before carbon raw material add-on, carbonate mends carbon raw material burn out rate, enter stove coal factor of created gase and add the former dry distillation gas composition that carbonate mends before carbon raw material can record in advance according to the small coke oven test (as 40kg small coke oven) with under gas retort same process condition that enters stove coal.

Calculation formula is as follows:

Wherein: M s---the burn out rate of carbonate, wt%;

V r---dry enter stove 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%;

The hydrogen-carbon ratio of synthetic gas before R---alkane transforms, 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, entering stove 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 coals 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 enters stove coal can be by making side dress (abbreviation is made firm by ramming) firm by ramming, the non-two kinds of modes of top dress (being called for short top dress) of making firm by ramming pack gas retort into; Make firm by ramming and require into stove coal index: fineness (≤3mm) >=85%, adhesive index=35~65; Top reload request enters stove 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, recovery of chemical products operation adopts the general method of current dry distillation gas: tar removing adopts electrical tar precipitator; Desulfurization (wet method) adopts modified ADA method, PDS+ tannin extract method 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 and filter or Temp .-changing adsorption (TSA); Thick desulfurization and smart desulfurization adopt dry desulfurization; Organosulfur transforms hydrocracking or the hydrolysis technology of adopting; The sweetening agent that described dry desulfurization uses comprises one or more in ferric oxide, manganese oxide, zinc oxide or gac; The catalyzer that described hydrocracking uses comprises one or more in iron molybdenum, nickel molybdenum and cobalt molybdenum hydrogenation catalyst; The catalyzer that described hydrolysis uses comprises normal temperature or the agent of middle temperature tempreture organic sulphur hydrolysis.

In above-mentioned embodiment, alkane conversion procedure 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; The conventional absorption agent of hydramine method comprises 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

Implement a kind of method of producing synthetic oil through autonomous benefit carbon take dry distillation gas as raw material, described in it, the concrete steps of method are as follows:

Raw material limestone ore deposit composition (wt%): CaO 54.3%, burn out rate 42.7%, impurity 3.0%.

Raw material enters stove coal charge composition (wt%): enter stove coal and coordinated and formed by the coking coal of 30% lean coal, 35% 1/3 coking coal, 20% rich coal and 15%; 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: enter stove coal and record 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 ℃, is down to normal temperature through quenching): entering stove coal factor of created gase is 353.4 Nm 3/ t; Adding carbonate mends in the front dry distillation gas of carbon raw material: 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 transforms, hydrogen-carbon ratio R, by 1.35, mends by above-mentioned carbonate the 29.0wt% that the known limestone mine add-on of carbon raw material add-on calculation formula is furnace coal weight.

Dry limestone mine, through thick broken, dry grinding, is made to breeze granularity≤80 order; Be added in stove coal by the 29.0wt% of furnace coal weight, mix rear employing top dress mode and pack gas retort into; By isolated the mixture charge in gas retort air heating continuous heating 24h, furnace charge core temperature reaches after 1100 ℃, after the furnace charge of red heat is come out of the stove, is down to normal temperature through quenching operation, then is 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, through electrical tar precipitator tar removing, the wet desulphurization of HPF method, sulfuric acid absorption method wash ammonia, washing oil absorption process is washed after 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 of mending after carbon.

The clean dry distillation gas of mending after carbon transforms and middle temperature zinc oxide essence desulfurization even depth cleaning section through TSA pre-treatment, the conversion of one-level iron molybdenum hydrogenation organosulfur, coarse iron oxide desulfurization, secondary iron molybdenum hydrogenation organosulfur again, total sulfur=0.084ppm; Then through alkane conversion procedure, adopt pure oxygen catalytic partial oxidation technique, under nickel catalyzator and 980 ℃ 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%; Remove CO finally by MDEA decarbonization process 2, CO 2=0.03%.Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transforms 2/ CO=2.0~2.06, mean value is 2.03, meets the synthetic benefit carbon requirement of synthetic oil, 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, under 230 ℃, 3.0MPa and the catalyst based condition of Fe, in paste state bed reactor, generate thick synthetic oil, then through oil purification operation, obtain take diesel oil as main synthetic oil product (diesel oil accounts for 72%, and all the other are LPG, petroleum naphtha etc.).

Embodiment 2

Dolomite mineral composition (wt%): CaO 30.4%, MgO 21.7%, burn out rate 47.4%, impurity 0.46%.

Entering stove coal is coordinated and is formed by the coking coal of 30% lean coal, 35% 1/3 coking coal, 20% rich coal and 15%; Its quality index (wt%): V adf30.0%, A d13.5%, FC d60.6%, S t,d0.67%, adhesive index=74, fineness (≤3mm)=73.6%.

Entering stove 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 ℃, is down to normal temperature through quenching): entering stove coal factor of created gase is 353.4 Nm 3/ t; Adding carbonate mends in the front dry distillation gas of carbon raw material: 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 transforms, hydrogen-carbon ratio R, by 1.15, mends according to above-mentioned carbonate the 28.0wt% that the known dolomite mineral add-on of carbon raw material add-on calculation formula is furnace coal weight.

Dry dolomite mineral, through thick broken, dry grinding, is made to breeze granularity≤80 order; Be added in stove coal by the 28.0wt% of furnace coal weight, mix rear employing top dress mode and pack gas retort into; By isolated the mixture charge in gas retort air heating continuous heating 20h, furnace charge core temperature reaches after 1050 ℃, after the furnace charge of red heat is come out of the stove, is down to normal temperature through quenching operation, then is qualified solid cleaning fuel after screening.

In solid cleaning fuel, CaO and MgO content 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, through electrical tar precipitator tar removing, the wet desulphurization of PDS+ tannin extract method, sulfuric acid absorption method wash ammonia, washing oil absorption process is washed after 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 of mending after carbon.

The clean dry distillation gas of mending after carbon transforms and middle temperature zinc oxide essence desulfurization even depth cleaning section through TSA pre-treatment, the conversion of one-level iron molybdenum hydrogenation organosulfur, coarse iron oxide desulfurization, secondary iron molybdenum hydrogenation organosulfur again, total sulfur=0.078ppm; Then through alkane conversion procedure, adopt pure oxygen catalytic partial oxidation technique, under nickel catalyzator and 980 ℃ 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%; Remove CO finally by MDEA decarbonization process 2, CO 2=0.04%.

Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transforms 2/ CO=1.94~2.0, mean value is 1.97, meets the synthetic benefit carbon requirement of synthetic oil, 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 is through F-T synthesis procedure, under 240 ℃, 3.0MPa and the catalyst based condition of Fe, generates thick synthetic oil in paste state bed reactor; Through oil purification operation, obtain take diesel oil as main synthetic oil product (diesel oil accounts for 73%, and all the other are LPG, petroleum naphtha etc.) again.

Embodiment 3

Dolomite mineral composition (wt%): CaO 30.4%, MgO 21.7%, burn out rate 47.4%, impurity 0.46%.

Entering stove coal is coordinated and is formed by the coking coal of 30% lean coal, 35% 1/3 coking coal, 20% rich coal and 15%; Its quality index (wt%): V adf30.0%, A d13.5%, FC d60.6%, S t,d0.67%, adhesive index=74, fineness (≤3mm)=73.6%.

Entering stove 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 ℃, is down to normal temperature through quenching): entering stove coal factor of created gase is 353.4 Nm 3/ t; Adding carbonate mends in the front dry distillation gas of carbon raw material: 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 transforms, hydrogen-carbon ratio R, by 1.35, mends according to above-mentioned carbonate the 18.0wt% that the known dolomite mineral add-on of carbon raw material add-on calculation formula is furnace coal weight.

Dry dolomite mineral, through thick broken, dry grinding, is made to breeze granularity≤80 order; Be added in stove coal by the 18.0wt% of furnace coal weight, mix rear employing top dress mode and pack gas retort into; By isolated the mixture charge in gas retort air heating continuous heating 15h, furnace charge core temperature reaches after 950 ℃, after the furnace charge of red heat is come out of the stove, is down to normal temperature through quenching operation, then is qualified solid cleaning fuel after screening.

In solid cleaning fuel, CaO and MgO content 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, through electrical tar precipitator tar removing, the wet desulphurization of modified ADA method, sulfuric acid absorption method wash ammonia, washing oil absorption process is washed after 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 of mending after carbon.

The clean dry distillation gas of mending after carbon transforms and middle temperature zinc oxide essence desulfurization even depth cleaning section through TSA pre-treatment, the conversion of one-level iron molybdenum hydrogenation organosulfur, coarse iron oxide desulfurization, secondary iron molybdenum hydrogenation organosulfur again, total sulfur=0.089ppm; Then through alkane conversion procedure, adopt pure oxygen catalytic partial oxidation technique, under nickel catalyzator and 980 ℃ 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%; Remove CO finally by MDEA decarbonization process 2, CO 2=0.02%.

Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transforms 2/ CO=2.06~2.12, mean value is 2.09, meets the synthetic benefit carbon requirement of synthetic oil, 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 is through F-T synthesis procedure, under 245 ℃, 3.0MPa and the catalyst based condition of Fe, generates thick synthetic oil in paste state bed reactor; Through oil purification operation, obtain take diesel oil as main synthetic oil product (diesel oil accounts for 71%, and all the other are LPG, petroleum naphtha etc.) again.

Embodiment 4

Limestone mine composition (wt%): CaO 54.3%, burn out rate 42.7%, impurity 3.0%.

Entering stove coal is coordinated and is formed by the non-caking coal of 30% weakly caking coal, 40% long-flame coal, 20% gas-fat coal and 10%; Its quality index (wt%): V adf35.0%, A d13.5%, FC d56.2%, S t,d0.84%, adhesive index=40, fineness (≤3mm)=86.5%.

Entering stove 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 ℃, is down to normal temperature through quenching): entering stove coal factor of created gase is 305.3 Nm 3/ t; Adding carbonate mends in the front dry distillation gas of carbon raw material: 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 transforms, hydrogen-carbon ratio R, by 1.01, mends according to above-mentioned carbonate the 25.6wt% that the known limestone mine add-on of carbon raw material add-on calculation formula is furnace coal weight.

Dry limestone mine, through thick broken, dry grinding, is made to breeze granularity≤80 order; Be added in stove coal by the 25.6wt% add-on of furnace coal weight, mix the rear employing mode of making firm by ramming and pack gas retort into; By isolated the mixture charge in gas retort air heating continuous heating 12h, furnace charge core temperature reaches after 900 ℃, after the furnace charge of red heat is come out of the stove, is down to normal temperature through quenching operation, then is 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, through electrical tar precipitator tar removing, the wet desulphurization of HPF method, sulfuric acid absorption method wash ammonia, washing oil absorption process is washed after 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 of mending after carbon.

The clean dry distillation gas of mending after carbon transforms and active-carbon finely desulfurization even depth cleaning section through TSA pre-treatment, the conversion of medium temperature hydrolyzation organosulfur, coarse iron oxide desulfurization, one-level iron molybdenum hydrogenation organosulfur again, total sulfur=0.077ppm; Then through alkane conversion procedure, adopt pure oxygen catalytic partial oxidation technique, under nickel catalyzator and 980 ℃ 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%; Remove CO finally by MDEA decarbonization process 2, CO 2=0.03%.

Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transforms 2/ CO=1.95~2.01, mean value is 1.98, meets the synthetic benefit carbon requirement of synthetic oil, 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 is through F-T synthesis procedure, under 245 ℃, 4.0MPa and the catalyst based condition of Co, generates thick synthetic oil in paste state bed reactor; Through oil purification operation, obtain take diesel oil as main synthetic oil product (diesel oil accounts for 74%, and all the other are LPG, petroleum naphtha etc.) again.

Embodiment 5

Dolomite mineral composition (wt%): CaO 30.4%, MgO 21.7%, burn out rate 47.4%, impurity 0.46%.

Entering stove coal is coordinated and is formed by the non-caking coal of 30% weakly caking coal, 40% long-flame coal, 20% gas-fat coal and 10%; Its quality index (wt%): V adf35.0%, A d13.5%, FC d56.2%, S t,d0.84%, adhesive index=40, fineness (≤3mm)=86.5%.

Entering stove 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 ℃, is down to normal temperature through quenching): entering stove coal factor of created gase is 297.7 Nm 3/ t; Adding carbonate mends in the front dry distillation gas of carbon raw material: 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 transforms, hydrogen-carbon ratio R, by 0.87, mends according to above-mentioned carbonate the 24.0wt% that the known dolomite mineral add-on of carbon raw material add-on calculation formula is furnace coal weight.

Dry dolomite mineral, through thick broken, dry grinding, is made to breeze granularity≤80 order; Be added in stove coal by the 24.0wt% of furnace coal weight, mix the rear employing mode of making firm by ramming and pack gas retort into; By isolated the mixture charge in gas retort air heating continuous heating 10h, furnace charge core temperature reaches after 800 ℃, after the furnace charge of red heat is come out of the stove, is down to normal temperature through quenching operation, then is qualified solid cleaning fuel after screening.

In solid cleaning fuel, CaO and MgO content 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, through electrical tar precipitator tar removing, the wet desulphurization of PDS+ tannin extract method, sulfuric acid absorption method wash ammonia, washing oil absorption process is washed after 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 of mending after carbon.

The clean dry distillation gas of mending after carbon transforms and active-carbon finely desulfurization even depth cleaning section through TSA pre-treatment, the conversion of medium temperature hydrolyzation organosulfur, coarse iron oxide desulfurization, one-level iron molybdenum hydrogenation organosulfur again, total sulfur=0.062ppm; Then through alkane conversion procedure, adopt pure oxygen catalytic partial oxidation technique, under nickel catalyzator and 980 ℃ 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%; Remove CO finally by MDEA decarbonization process 2, CO 2=0.04%.

Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transforms 2/ CO=1.90~1.96, mean value is 1.93, meets the synthetic benefit carbon requirement of synthetic oil, 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 is through F-T synthesis procedure, under 230 ℃, 4.0MPa and the catalyst based condition of Co, generates thick synthetic oil in paste state bed reactor; Through oil purification operation, obtain take diesel oil as main synthetic oil product (diesel oil accounts for 73%, and all the other are LPG, petroleum naphtha etc.) again.

Embodiment 6

Dolomite mineral composition (wt%): CaO 30.4%, MgO 21.7%, burn out rate 47.4%, impurity 0.46%.

Entering stove coal is coordinated and is formed by the non-caking coal of 30% weakly caking coal, 40% long-flame coal, 20% gas-fat coal and 10%; Its quality index (wt%): V adf35.0%, A d13.5%, FC d56.2%, S t,d0.84%, adhesive index=40, fineness (≤3mm)=86.5%.

Entering stove 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 ℃, is down to normal temperature through quenching): entering stove coal factor of created gase is 286.3 Nm 3/ t; Adding carbonate mends in the front dry distillation gas of carbon raw material: 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 transforms, hydrogen-carbon ratio R, by 0.84, mends according to above-mentioned carbonate the 27.0wt% that the known dolomite mineral add-on of carbon raw material add-on calculation formula is furnace coal weight.

Dry dolomite mineral, through thick broken, dry grinding, is made to breeze granularity≤80 order; Be added in stove coal by the 27.0wt% of furnace coal weight, mix the rear employing mode of making firm by ramming and pack gas retort into; By isolated the mixture charge in gas retort air heating continuous heating 6h, furnace charge core temperature reaches after 700 ℃, after the furnace charge of red heat is come out of the stove, is down to normal temperature through quenching operation, then is qualified solid cleaning fuel after screening.

In solid cleaning fuel, CaO and MgO content 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, through electrical tar precipitator tar removing, the wet desulphurization of modified ADA method, sulfuric acid absorption method wash ammonia, washing oil absorption process is washed after 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 of mending after carbon.

The clean dry distillation gas of mending after carbon transforms and active-carbon finely desulfurization even depth cleaning section through TSA pre-treatment, the conversion of medium temperature hydrolyzation organosulfur, coarse iron oxide desulfurization, one-level iron molybdenum hydrogenation organosulfur again, total sulfur=0.069ppm; Then through alkane conversion procedure, adopt pure oxygen catalytic partial oxidation technique, under nickel catalyzator and 980 ℃ 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%; Remove CO finally by MDEA decarbonization process 2, CO 2=0.03%.

Gained gaseous carbon element is supplemented, hydrogen-carbon ratio r=H after alkane transforms 2/ CO=1.93~2.0, mean value is 1.96, meets the synthetic benefit carbon requirement of synthetic oil, 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 is through F-T synthesis procedure, under 220 ℃, 4.0MPa and the catalyst based condition of Co, generates thick synthetic oil in paste state bed reactor; Through oil purification operation, obtain take diesel oil as main synthetic oil product (diesel oil accounts for 71%, and all the other are LPG, petroleum naphtha etc.) again.

Claims (7)

1. a method of producing synthetic oil take dry distillation gas as raw material through autonomous benefit carbon, described in it, method follows these steps to carry out:
(1) determine into the quality index of stove coal and be: FC d>=50%, V adf>=25%, A d≤ 25%, S t,d< 1.5%;
(2) determine that carbonate mends the burn out rate of carbon raw material, enters the factor of created gase of stove coal and the composition of former dry distillation gas;
(3) dry carbonate is mended to carbon raw material through thick broken, dry grinding, made breeze granularity≤80 order;
(4) ground carbonate benefit carbon raw material is added in stove coal and mixes, and obtains mixture charge, packs mixture charge into gas retort;
Medium temperature carbonization, carbonate is mended 8~28wt% that carbon raw material add-on is furnace coal weight;
High temperature carbonization, it is 10~30wt% of furnace coal weight that carbonate is mended carbon raw material add-on;
(5) by isolated the mixture charge in gas retort air heating, by thermolysis and superfluous H 2gas coupling is mended carbon;
Medium temperature carbonization continuous heating 6~12h, furnace charge core temperature rises to 700~900 ℃ gradually;
High temperature carbonization is continuous heating 12~24h, and furnace charge core temperature rises to 900~1100 ℃ gradually;
Then after the furnace charge of red heat being come out of the stove, be down to normal temperature through quenching operation, then after screening, be solid cleaning fuel;
(6) the waste dry distillation gas that gas retort heat-processed is overflowed, through tar removing, wet desulphurization, wash ammonia, wash after the recovery of chemical products operation of benzene, is the clean dry distillation gas of mending after 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 clean dry distillation gas after carbon again through pre-treatment, organosulfur transforms for the first time, thick desulfurization, organosulfur transforms and the deep purifying operation of smart desulfurization for the second time, total sulfur≤0.1ppm;
(8) through alkane conversion, 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, under 190~270 ℃, 1.0~4.5MPa and catalyzer condition, generates thick synthetic oil; Through oil purification operation, obtain take diesel oil as main synthetic oil product, wherein, diesel oil accounts for 70% again, and all the other are LPG and petroleum naphtha.
2. the method for claim 1, described in it, the add-on of carbonate benefit carbon raw material is calculated by following formula:
Wherein: M s---the burn out rate of carbonate, wt%;
V r---dry enter stove 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%;
Before R---alkane transforms, the hydrogen-carbon ratio of synthetic gas, is generally 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.
3. the method for claim 1, described in it, carbonate benefit carbon raw material is the one in Wingdale, rhombspar, spathic iron ore and magnesite.
4. method as claimed in claim 3, the negatively charged ion described in it in Wingdale, rhombspar, spathic iron ore and magnesite is [CO 3] 2-, positively charged ion is Ca 2+, Mg 2+or Fe 2+.
5. the method for claim 1, described in it, in 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%.
6. 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.
7. the method for claim 1, described in it, synthetic oil synthetic gas is through the synthetic synthetic oil product that can obtain take diesel oil as master of F-T, and wherein diesel oil accounts for more than 70%, and all the other are LPG, petroleum naphtha.
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CN101955784A (en) * 2010-09-27 2011-01-26 山东科技大学 Coking composite leaning agent and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1995291A (en) * 2006-01-05 2007-07-11 尹小林 Method for producing CO cleaning gas catalyzed by carbonate ore and carbon
CN101003359A (en) * 2006-12-14 2007-07-25 杨献斌 Method for preparing methanol synthesis gas by using coke oven gas to make hydrogen, and complementing carbon from water gas
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
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