CN101016469A - Production of marine diesel oil by middle and inferior quality bitumite and coproduction clean coal system processes and apparatus - Google Patents
Production of marine diesel oil by middle and inferior quality bitumite and coproduction clean coal system processes and apparatus Download PDFInfo
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- CN101016469A CN101016469A CN 200610095139 CN200610095139A CN101016469A CN 101016469 A CN101016469 A CN 101016469A CN 200610095139 CN200610095139 CN 200610095139 CN 200610095139 A CN200610095139 A CN 200610095139A CN 101016469 A CN101016469 A CN 101016469A
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Abstract
The invention discloses a clean coal new craft, which comprise the following steps: 1. adopting middle and low quality bituminite; proceeding quick hot exchange through the new craft; getting high yield and low temperature coal oil; 2. reacting with oxymethylene under diverse condition through new craft; producing diverse phenol resin and purified coke tar diesel oil; distilling with hot water vapor; getting 'marine diesel oil'; or proceeding hot vapor fires; getting diesel oil distillate; reacting with oxymethylene; purifying; getting the product of 'marine diesel oil'; 3. adding into cetane number additive--o-diethylaniline in this program; or adopting blending matter and o-diethylaniline; providing to cars; 4. processing retorting semi-coking to life form clean coal and industrial clean coal. This craft can realize the purpose of clean coal flackery.
Description
One, the historical background of project:
The commodity that do not have " marine diesel oil " this title on the market of China and countries in the world, the commercial Dissel oil that circulates on the current market, be by petroleum crude oil processing and few part by coal through hydrogenation liquefaction or through water-gas synthin product processed.
The present invention utilizes bituminous coal to pass through the special use " marine diesel oil " of high yield coalite tar processing ship use intermediate speed engine.Different with above-mentioned various operational paths, be in conjunction with the resources characteristic of China and promoting the use of of contemporary clean coal and the joint process route that designs.
China begins oil plant from the Great Leap Forward age and lacks, extensively carry out and produce diesel oil by all kinds of means, owing to utilize the characteristics (and the burnt mass discrepancy of each burnt kerosene is also big) of chemical ingredients of the coalite tar of coke making by indigenous methods then, cetane value is generally about in the of 35, serious for this fuel oil of automobile high-speed engine pinking in combustion processes (engine knock), emit white cigarette (combustion time is short, can burn Wan) engine overheat in the exhaust, power does not reach specified.Again because fraction of diesel oil is wide for many years, even uses and only filter simple measures and purify, the oil product gum level is too high, and is all unresolved for a long time, and very fast quilt " is killed " after presenting nozzle in the use and stopping, and cold car can't start again; Make engine shorting-out for automobile because of the oil plant factor, can stop on the way at any time; And in the ship navigation if will cause serious safe disaster because of the oil plant factor is flame-out,, when beating the beach, reach and run under the abominable meteorological conditions in the ocean navigation as inland navigation, the engine of ship definitely can not stop working; Therefore " marine diesel oil " specification of quality is stricter than automobile-used " diesel oil ".It must be except that cetane value, any index all will meet GB252-87, and enterprise's mark (according to user's the index that requires), but coalite tar " marine diesel oil " is very to share for middling speed bunker oil machine, practice use in a few years is confirmed, I utilize 302 factories and colliery, Yongfu local method tar in 1980 north of the Changjiang River county synthetic oil factory, supply with several fleets and use for 2 years with 30 tons scale production in every month; But, stopped coke making by indigenous methods, thereby local method low temperature kerosene has not been originated along with country strengthens the environmental improvement measure.
Never utilize coalite tar to make commercial Dissel oil stream on the Chinese market and pass through, do not see the report of success in all relevant refining data as yet, information interchange all under test, the termination of coke making by indigenous methods in addition again, people have forgotten this channel.
Two, the purpose of this project invention:
1, low quality coal solves China's " marine diesel oil " and produces, the petroleum crude oil import that minimizing is annual tens million of tons by high yield coalite tar operational path in the use;
2, remaining 80% meal shape semicoke is used for clean coal production after having refined coalite tar, solves the popularization of clean coal for many years;
3, make each colliery or coal processing enterprise in the processing of this project, can obtain 100～300 yuan of profits, thereby make above-mentioned binomial explained hereafter at the coal district smooth implementation from coal per ton.
4, " cleaned coal " is valuable resource, be used for coking, hydrogenation liquefaction, FT is synthetic all is not the purposes of its best; The present invention is based upon to make Chinese reserves maximum, the most general in, low quality coal (stating in addition) refines coalite tar and is processed into " marine diesel oil " and clean coal production;
5, current domestic many enterprises all stretch out one's hand to charge to state revenue and expenditure and invest liquidation of coal oiling engineering, have information to warn 3,000,000 tons of following scales, do not have the possibility of the profit and the fund of recovery! The present invention makes coal processing enterprise comprise the colliery, produces profit preferably; And big processing enterprise's all profitable (stating in addition) on a small scale, producer's capital investment does not need country to make non-profit making input, because enterprise has profit to increase the state revenue and expenditure receipts on the contrary.
Technology of the present invention is discussed:
(1) solid thermal carriers bituminous coal low-temperature pyrolysis technology: (seeing also Figure of description)
Pressurized air 1 is through interchanger heating tube 2,3 enter interchanger 11, enter 5 riser tubes 14 by pipe, the semi-coke powder burning is heated to 700 ℃, to reservoir 7, through output tube 7 ' enter in proportion mixing tank 9, to send in the mixing tank 9 to mix through 8 ratio handling machinerys at this bituminous coal powder and twin shaft is stirred the follower rotating speed be adjusted to suitably to hold time to optimum regime and enter in the dry distiller 10 with the semicoke thermophore, the residence time transfers to going out oil vapour the best to be determined with oil mass.Tar steam transfers to little negative pressure can dirtyly smoothly be degree to the semicoke sedimentation pipe, negative pressure is to be added by 14 separators, by the water spray vacuum feed.Negative pressure is to be easy to enter cooling condensation in the interchanger by oil vapour in the dry distiller, and negative pressure is unlikely the effusion thermal decomposition product in mixing tank.Malleation coal gas enters gas storage holder.
(2) coalite tar dewaters through layering, with 200 ℃ of superheated vapours, the low fraction of stripping and take off moisture content (keeping rough vacuum to strengthen vacuum gradually) in the residual oil, and progressively strengthen the superheated vapour inlet, superheated vapour is progressively brought up to 500 ℃ by 200 ℃, final what value that keeps of tower top temperature is determined the oil distillation decision by the workshop chemical examination, enter interchanger by overhead product and produce secondary low-voltage steam 0.5-1 gauge pressure, send superheater, the effusive coolant water temperature of second interchanger keeps 70-80 ℃, does the steam boiler water inlet.Separate semi coking tar and not condensing gas by the 3rd condenser through vapour liquid separator again, store, carry out gas processing through steam chest; Compress 5 gauge pressures through the first step, separate after cooling off, gas is compressed to 17 gauge pressures through the second stage, separates dry gas for this enterprise heating thermal source, can sell combustion gas when extensive; Gained C
4, C
3Making liquefied gas handles; Processing to each gas fraction when extensive need be perfect, relates to safety first, second environmental protection, and three is a considerable income, because of coal per ton can generate 30～50m
3Gas can be supported utilization.1000 tons of coals of imagination processing have just had 3～50,000 m
3Coal gas!
(3) the refining purification of oil product is different from the classical way in the oil refining process, also be different from the hydrofining of modernized chemical industry, the latter is difficult to realize in general enterprise, middle and small scale is lost more than gain, adopt the characteristics of oil product self composition to make and its chemical reaction with formaldehyde, get the synthetic resins of several different purposes, thereby make tar acid and unsettled composition remove oil product and be made with extra care, purify through reaction, this is a novel process!
Oil Production hydrofining more than 10,000 tons also still can be carried out, and the hydrogen supply can Mining primary external-heat, stove, can make carbon source with wooden carbon, gasification temperature is lower than coke, with interior external-heat superheated vapour greater than 900 ℃ of gasifications, equipment is made body of heater with the modern material high temperature resistant stainless steel, less investment saves trouble, and 2/3 heating power can reclaim by heat exchange, energy consumption is also low, and wooden carbon can adopt the agricultural production by product.
(4) gained semicoke:
1, process characteristic:
A. the semi-coke powder interpolation contains magnesian chalk or lime white, becomes clean life moulded coal through die mould;
B. semi-coke powder adds high temperature desulfuration agent (existing many scientific researches enterprise are in one's power produced), manufacture clean moulded coal;
C. adopt the middle low quality coal of dry method jigging to carry out the semicoke that high yield solid thermal carriers heat exchange destructive distillation produces and increase temperature sweetening agent, cure again to relevant temperature with the shaping of high-pressure molding machinery, dry method cool off formed coke.
If yet the semicoke that 2 these technologies are produced cost absorption on semi coking tar, semicoke only maintains on the raw coal price, is used for being processed into honeycomb briquette, semicoke profit per ton as can be seen is more than 300 yuan! Use instead if no longer add loess and to contain the magnesite mortar and make clean coal, calorific value still maintains more than 4500 kilocalories, the user very welcomes, no sulfurous gas cigarette, firepower is tempered greatly, becomes ignitable honeycomb briquette if add part again, and then the user no longer " carries on the back fire " every day, can save 90 honeycomb briquettes in every month, also play energy-conservation effect.
If 3, about promoting the use of of the clean coal of industry semicoke heated and is pressed into moulded coal behind the sweetening agent for raw coal user burning, refusal uses as long as the constant enterprise of price has no reason, the quality of clean moulded coal on the other hand, calorific value can guarantee unlike raw coal, the supplier is none not a large amount of filling colliery powder over the years, earn evil mind money, reach the degree that is difficult to forbid.Because bituminous coal is used for producing semi coking tar, can't be also in the raw coal can not the blending coal gangue, the calorific value of semicoke just might be stablized, and it also is possible that the user accepts suitable raising, and problem is the existing big profit of processing in overall system process, clean coal price markup also should be subjected to the restriction of national price department, retrained by market control, price markup back user can be in other place's buying, and the semicoke machining object is sold with former coal price, existing profit, the colliery also still can be accepted.
4, industrial clean formed coke: it is with instead of coke or part coke market, tentatively outside the difficult acceptance of iron-smelting blast furnace, other many industries all can be accepted under the condition that significantly price reduces.
Because the calorific value of formed coke requires high, the ash fusion point height, non-volatility, the semicoke that intensity height, middle inferior coal will obtain with dry method jigging (may will rise to 10-12% but low-temperature pyrolysis is coal-tar middle oil by original 8-10%, also be very favourable) before low-temperature pyrolysis, make additive with the coal tar pitch that is difficult to now utilize, through the compression moulding of high pressure shaper, through curing (natural roasting), qualified again to product.This complete processing, a maximum value is low quality coal rather than " coking coal cleans " in utilizing, the coal source is general, price almost is at half, and product cost is just low, and profit is just big, at most not as good as 2/3 of coke 1100-1200 unit, profit at least also has per ton more than 300 yuan price.
So totally say low quality coal production " marine diesel oil " coproduction " clean coal " in the utilization, be a process engineering that is worthy to be popularized.
Five, operational path characteristics of the present invention:
1, select for use domestic reserves maximum, the middle low quality coal that everywhere all has is made raw material; And other technology all adopts high-quality, high volatilization, low ash coal, low sulphur coal; High-quality bituminous coal is a kind of raw material of preciousness, and oiling is not its best value; The qualitative characteristics of middle inferior coal: calorific value is at 4000-5000 kilocalorie/kg; Ash is more than 30%; Fugitive constituent between 25-30%, the sulphur height; Combustion activity is low, is commonly called as to start to exchange fire slowly, and coking property is poor, thermolysis performance " blunt " during destructive distillation, (aluminium rice steamer test oil length is low, selects the bituminous coal greater than 6-8% for use).
2, in order to improve tar productivity and tar acid; Operating parameters is different from foreign data a bit:
1. the granularity of coal adopts 1-3mm (adopting 4-10mm abroad), helps reducing height 1/3 at riser tube; Pressurized air, pressure reduce, and bituminous coal grain surface-area is big, and the utilization ratio of warm air oxygen is improved relatively, and the pressurized air consumption reduces, and energy consumption reduces; 2. because granularity is little, obviously accelerate with thermal barrier heat exchange heat transfer rate, the residence time is shorter in the twin shaft mixing tank; The residence time prolongs in dry distiller, taper destructive distillation separator, and cylindrical shell lengthening (tapering reduces), negative pressure (water jet pump) minute-pressure is played at destructive distillation device separator 14 places in the operation, is no more than the 20mm water column in mixing the grain device, helps oil vapour and collects.Improve tar productivity.
3. the thermal barrier temperature should not surpass 600 ℃, and temperature should not surpass 360 ℃ in the dry distiller, can obtain the tar preferable quality and make the little diesel oil of jarring; The feed ratio of thermophore semicoke obviously is greater than the quantity of shale retorting.
3, coalite tar processing, the marine diesel oil process characteristic;
1. full fraction is kept 70 ℃ and is left standstill to the tar water layering in storage tank, separate.
2. progressively be warming up to the stripping tower cat head by hot steam (200 ℃) and keep 120 ℃, oil mass is back (the low temperature fraction can be processed into all kinds of SOLVENTS oil) less, and superheated vapour is warming up to 500 ℃, need not reflux for 300 ℃ by dominant discharge to cat head, the stable fraction of collecting is till oil mass decline.Be different from alternate manner and add thermal distillation, oil quality is good; Lighter color after following purification and stablizing.
3. separate full fraction in the water-and-oil separator, it is adopted different ph values with formaldehyde solution (different concns), use Ba (OH) at first
2, NaOH carries out the segmentation resinifying, separating treatment; Thereafter handle with weak acid, strong acid segmentation resinifying, each all different resol of availability matter is used for film forming matter modified resin again, thermosetting resin, and the vulcanization of rubber strengthens resin, and the arylamine modified phenolic resins, extensive stock; This also is a unique distinction in the oil purification technology; Also can adopt crude tar oil after adding filter material and carrying out fine filtering,, behind the separation resin, use superheated vapour with formaldehyde segmentation reaction, distill " marine diesel oil "; This is more favourable than make with extra care purification with classical soda acid repeated treatments, and cost is low, and appurtenant is worth high, and oil quality is good, and " not killing oil nozzle " do not corrode skin, is used for Marine Medium-speed Diesel Engine, and burning is steady, and engine knock does not emit white cigarette, can add various properties-correcting agent.
4, can improve cetane value to 45, steam supply overall height speed engine uses, and can adopt following measures:
A. utilize byproduct o-nitroethylbenzene in several families big pharmaceutical factory production of chloramphenicol, change the former o ethyl aniline that gets with iron powder, dark oil liquid need not rectifying, directly can join in the coal tar diesel oil, consumption 1-3%, use in car engine, use normally below idling and 2800 is changeed, the tar diesel oil that has has the jarring phenomenon when being higher than 2800 commentaries on classics acceleration operations;
Nobody used o ethyl aniline to make ignition dope in history.
B. utilizing at the bottom of each refinery tower oil and lube cut to be blended in the coal tar diesel oil 10-20% increases cetane value and can make positive 10# diesel oil because of adding normal paraffin;
C. with market on " diesel oil " (cetane value general all more than 55) each 1/2 or blending in 1: 3, automobile normally uses, and can both play the purpose that reduces Imported oil crude oil.
Six, for realizing that the best mode of the present invention is: set up an engineering demonstration enterprise.
Calendar year 2001 is a group leader unit by State Planning Commission, and State Scientific and Technological Commission and economic and commercial committee are Deputy Chief of Branch unit, and 13 ministries, commissions and bureaus of State Council strive for realizing this process sequence production for the group member has set up " clean coal technology is promoted planning leading group " under the leader of State Planning Commission.
Claims (6)
1, low quality coal obtains the high yield coalite tar, (whole temperature is no more than 400 ℃) through solid thermal carriers Rapid Thermal exchange low-temperature pyrolysis in the utilization; Be reprocessed into " marine diesel oil " fraction with the superheated vapour novel process;
2, " marine diesel oil " fraction is made with extra care employing formaldehyde PH with novel process; The condensation resin of reaction hierarchical segmented generation resol of different nature and other unsaturated composition under the POH value condition, thereby oil product is removed " diesel oil " character objectionable impurities, various resins have different market, purposes simultaneously, as film forming matter, thermosetting resin, the vulcanization of rubber strengthen resol and to the STUDY ON THE MODIFICATION OF PENOLIC RESIN thing of arylamine formaldehyde resin etc.
3, utilize low-temperature pyrolysis gained semicoke, add chalk, contain magnesian lime, high temperature desulfuration agent is produced various clean moulded coals: life clean moulded coal, industrial clean moulded coal, clean formed coke.
4, clean formed coke production: low quality coal in the employing, behind the dry method jigging, produce semi coking tar and high heating value semicoke through destructive distillation again, semicoke is made binding agent through adding high temperature desulfuration agent and coal-tar pitch (the domestic thing that is difficult to processing), gets the formed coke of instead of coke through roasting with high-pressure molding.
5, " marine diesel oil ", three kinds of clean coals are the serial composite technologies of a cover, and variety production does not possess the profit condition separately; The ignition dope o ethyl aniline of " marine diesel oil " is an original creation product of the present invention, and market does not have;
6,1,2,3,4,5 listed products of " marine diesel oil " trade name and claim and system process are this patent protection domain.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610095139 CN101016469A (en) | 2006-09-21 | 2006-09-21 | Production of marine diesel oil by middle and inferior quality bitumite and coproduction clean coal system processes and apparatus |
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| CN 200610095139 CN101016469A (en) | 2006-09-21 | 2006-09-21 | Production of marine diesel oil by middle and inferior quality bitumite and coproduction clean coal system processes and apparatus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334323B (en) * | 2020-03-18 | 2021-08-06 | 深圳前海新域能源科技有限公司 | Elution tower and elution method of elution tower on full-range coal tar |
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2006
- 2006-09-21 CN CN 200610095139 patent/CN101016469A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111334323B (en) * | 2020-03-18 | 2021-08-06 | 深圳前海新域能源科技有限公司 | Elution tower and elution method of elution tower on full-range coal tar |
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Open date: 20070815 |