CN105001900B - A kind of technique through methanol synthesized gasoline for coke-stove gas - Google Patents
A kind of technique through methanol synthesized gasoline for coke-stove gas Download PDFInfo
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Abstract
A kind of technique through methanol synthesized gasoline for coke-stove gas is coke-stove gas and oxygen is first allocated supersaturated vapor into and entered in converting coke oven gas stove combustor and carries out combustion reaction and conversion reaction, after conversion, gas is compressed carries out methanol synthesis reaction, reacting gas carries out separating methanol, the a part of gas discharged from methanol separator top is back to synthesic gas compressor group, another part gas carries out artificial oil reaction, and crude carbinol liquid phase carries out the reaction of methanol artificial oil from after the discharge of methanol separator bottom, synthesis oil product carries out Oil-gas Separation, the oil phase isolated enters in oil product separator, fuel gas is obtained after separating, liquefied petroleum gas, heavy oil and gasoline products.The present invention has the advantages that technological process is simple, equipment investment is few and energy consumption is low.
Description
Technical field
The invention belongs to the technique that a kind of coke-stove gas is converted into gasoline products through methanol.
Background technology
China has rich coal, the energy resource structure of oil-poor and few gas, and the imbalance between supply and demand of especially oil is very prominent.2013
The external dependence degree of China's oil reached 58.1% it is contemplated that the external dependence degree of the year two thousand twenty China's oil be up to 65% so that
National energy security, economic security and social safety will face big challenge.Therefore, development substitute energy source for petroleum is to alleviate oil
Imbalance between supply and demand and the important channel guaranteeing national security.
Methanol converts gasoline processed and was proposed in patent US3931349 in 1976 by Mobil company of the U.S. earliest, specially
First by methanol in Cu/Al2O3On catalyst, dehydration forms dimethyl ether, is then converted into dimethyl ether under the catalytic action of ZSM-5
High-octane gasoline products.A kind of technological process disclosed in Chinese patent ZL200610048298.9 is shorter and operation is simpler
One-step method preparing gasoline by methanol technique, methanol is converted into gasoline products on modified zsm-5 zeolite by this technology.Above-mentioned
The successful exploitation of two kinds of technique for preparing gasoline by methanol and industrial applications not only provide technical strategies for oil replacement,
And compared with the oil replacement technology such as DCL/Direct coal liquefaction and coal indirect F-T liquefaction, preparing gasoline by methanol has process is simple, technology becomes
The advantages of ripe reliability and yield of gasoline are high, becomes the focus of recent year concern.
China is coke production maximum in the world, consumption and exported country.2012, China's coke output reached 4.43 hundred million t,
If producing 430m by producing one ton of coke3Coke-stove gas calculate, the coke-stove gas of only this year by-product is just up to 190,500,000,000 m3,
Wherein 70% about coke-stove gas is used for coke oven heating and domestic gas, and remaining nearly 57,000,000,000 m3Coke-stove gas is not sharp
With causing the serious wasting of resources and environmental pollution.The successful exploitation of coke-stove gas methanol technology achieves coke-stove gas
Recycling, not only create certain economic benefit, and there is good environmental benefit and social benefit.But with
Coke-stove gas utilizes the diversification of technology, the real price nearly 0.5 yuan/Nm of coke-stove gas3, simultaneously take account of methanol market
Production capacity is seriously superfluous, and methanol prices are decreased obviously, therefore the absolute profit of industrial coke-stove gas methanol project is seriously shunk, especially
Compare with respect to coke-stove gas CNG with LNG, the relative profit of preparing methanol from coke oven gas is lower.
In view of the market status of domestic petroleum imbalance between supply and demand, the rise of coke-stove gas real price and methanol production capacity surplus,
If the methanol preparing coke-stove gas is further converted to gasoline products by technique for preparing gasoline by methanol, it is not only able to alleviate stone
Oil shortage and the problem of methanol surplus, and the economic benefit of coke-stove gas utilization can be lifted further.But it is existing industrial
Preparing gasoline by methanol technique is both needed to be used refined methanol (methanol concentration >=99.9%) as raw material so that the first prepared by coke-stove gas
Alcohol need to pass through refining methanol unit, and single coke-stove gas methanol has after-heat and wastes, and methanol converts gasoline processed
The contradiction of shortage of heat, leads to final technology to have the shortcomings that complex process, equipment investment be big and high energy consumption, simultaneously takes account of
The production scale through methanol-fueled CLC oil for the coke-stove gas is limited, extremely sensitive to the problems referred to above present in technique.Therefore, develop one
The monoblock type technique through methanol-fueled CLC oil for the coke-stove gas that kind technological process is simple, equipment investment is little and energy consumption is low has important
Meaning.
Content of the invention
The purpose of the present invention is to develop the coke-stove gas that a kind of technological process is simple, equipment investment is few and energy consumption is low through methanol
The integrated artistic of synthetic gasoline.
For reaching above-mentioned purpose, inventor first passes through in lot of experiments methanol impurity content, dopant species and follows
Ring gas becomes the impact to methanol synthesis catalyst activity, selectivity and stability for the grading factors；Then according to above-mentioned experimental data
Report, passes through that substantial amounts of simulation calculates and experience in design for many years is it is proposed that a kind of coke-stove gas is inverted, conjunction further
Become air pressure contracting, methanol-fueled CLC, preparing gasoline by methanol and the detached integral process of oil product, this technique passes through overall material and energy
Coupling, not only enormously simplify technological process, and decreases equipment investment and overall energy consumption, further increases coke-stove gas
Using economic benefit.
A kind of integrated artistic through methanol-fueled CLC oil for the coke-stove gas of the present invention, comprises the steps：
(1) coke-stove gas after purified first allocates supersaturated vapor into, then is converted with oven gas by coke oven air preheater
Outlet of still gas heat exchange, after through burning preheating furnace heat further after enter coke oven gas converter in, in space division system
After oxygen allocates supersaturated vapor into, enter in converting coke oven gas stove combustor from top and first carry out burning with coke-stove gas instead
Should, the gaseous mixture after then burning enters from top to bottom in converting coke oven gas furnace catalyst layer and carries out conversion reaction, after conversion
Gas first inverted stove waste heat boiler from after the discharge of bottom reclaims heat, then through coke-stove gas preheater and coke-stove gas heat exchange,
Then entered in gas-liquid separator after converting Gas Cooler cooling, separate the fresh water (FW) obtaining and arrange from gas-liquid separator bottom
It is sent to reburner waste heat boiler by-product middle pressure steam after going out and mixing with the fresh water (FW) from oil gas water separator, one of by-product
Point middle pressure steam enters after forming supersaturated vapor after burning preheating furnace is heated, respectively with purify after coke-stove gas and be derived from
Oxygen mix in space division system enters the top of coke oven gas converter, and another part middle pressure steam provides vapour for methyl alcohol vaporizing device
Change heat, separate the gas phase obtaining and discharge from gas-liquid separator, and be mixed into conjunction with circulating air after the further desulfurization of desulfurizer
Become in air compressor group and be pressurized；
(2) the reacting gas heat exchange that the mixed gas after being pressurized are discharged with methanol reactor bottom through synthesis air preheater
Afterwards, enter in methanol synthesis reactor from top and carry out methanol synthesis reaction, reacting gas is arranged from methanol synthesis reactor bottom
Go out, first through synthesis air preheater heat exchange, then enter in methanol separator after evaporative type cooler condensation, gas phase is from separating methanol
Device top is discharged and is back to synthesic gas compressor group, another part gas with the gas mixing rear portion gas from flash tank
Body is first mixed in synthesis oil reactor with the crude carbinol after gasification after synthesis oil reactor import air preheater preheating, and
The crude carbinol liquid phase being made up of methanol, fusel, water and lower carbon number hydrocarbons etc. enters methanol filter from after the discharge of methanol separator bottom
In, through acid-exchange resin filter after enter flash tank carry out flash separation, a small amount of gas phase from flash tank top discharge with
Methanol separator tower overhead gas mixes, and crude carbinol liquid phase is discharged from flash drum bottom；
(3) crude carbinol coming from flash tank is first through methanol preheater preheating, then gasified by methyl alcohol vaporizing device, after through first
After alcohol superheater is overheated, enters in synthesis oil reactor with the gas mixing from artificial oil Reactor inlet air preheater and carry out
Artificial oil reacts, and synthesis oil product is divided into two strands of materials, and wherein first strand material is through synthesis oil inlet gas heat exchanger and from first
Enter in oil product air cooler after the gas converting heat that alcohol separator comes, and second strand of material first reclaims heat through artificial oil waste heat boiler
Amount, then through methanol superheater and crude carbinol steam heat-exchanging, after change with the liquid phase crude carbinol from filter through methanol preheater
Merge with first strand of material after heat, the synthesis oil product after merging is further after oil product air cooler and oil product cooler cool down
Enter in separator, gas phase is discharged and after recycle gas compressor supercharging from oil gas water separator top, a part of gas conduct
Circulating air is back to synthesic gas compressor group, the fuel gas that another part is isolated with oil product separator mix being sent to burning preheating
Burn in stove, the fresh water (FW) condensing out is discharged from oil gas water separator bottom and mixed with the fresh water (FW) from gas-liquid separator
After be sent to byproduct steam in reburner waste heat boiler, and the oil phase isolated enters in oil product separator, obtains fuel after separating
Air-liquid liquefied oil gas (LPG), heavy oil and gasoline products.
After purified and desulfurization, the volume of coke-stove gas consists of H as above250～60%, CO 5%～8%,
CO21.5～4%, CH423%～27%, N23～7%, C2Above unsaturated hydrocarbons 2～4%.
Coke oven gas converter as above is fixed bed adiabatic reactor, and its reaction pressure is 2.0～2.5MPa, coke oven
Gas inlet temperature is 600～700 DEG C, and reburner is divided into top combustor and bottom conversion chamber, and lower floor's conversion chamber filling is up and down
Two-layer catalyst, upper strata is Z205 type reforming catalyst, and its admission space accounts for 15～25Vol% of beds cumulative volume；
Lower floor is Z204 type reforming catalyst, and admission space accounts for 75～85Vol% of beds cumulative volume, two kinds of catalyst by
Sichuan Tianyi Science ＆ Technology Co., Ltd produces；
The volume ratio of the coke-stove gas and oxygen entering coke oven gas converter as above is 4.5～5.5, and reburner gives up
It is partly into burning preheating furnace in the middle pressure steam that heat boiler produces and produces supersaturated vapor, supersaturated vapor passes through to join respectively
Enter coke-stove gas and be back in reburner with the mode allocating oxygen into, wherein control the volume ratio of supersaturated vapor and coke-stove gas
For 0.15～0.25, supersaturated vapor is controlled to be 3.0～3.5 with the volume ratio of oxygen, remaining another part middle pressure steam send
It is used for methanol gasifying toward methyl alcohol vaporizing device.
Methanol synthesis reactor as above adopts shell-and-tube isothermal reactor, and its reaction pressure is 5.7～6.5MPa,
Reaction temperature is 240～260 DEG C, and gas space velocity is 15500～20000L/ (Kg h).
C306, C307 catalyst that the catalyst of methanol-fueled CLC as above is developed for Research Institute of Nanjing Chemical Industry Group, Dalian
One of C302 catalyst of the RK-5 catalyst of Rake Science and Technology Ltd. production or the exploitation of southwestern chemical design institute.
The circulating air from methanol separator and oil gas water separator entering in synthesic gas compressor group as above
Sum is 5.0～6.0 with the volume ratio from desulfurizer gas phase.
The gas phase that methanol separator top as above is discharged with merge from the gas phase that flash tank is discharged after for two
Point, wherein it is back to the gas of synthesic gas compressor group with the gas volume entering methanol synthesis reactor ratio for 2.5～3.0.
The CT151 type acid-exchange resin that in methanol filter as above, filling Piao Laite company produces, warp
Filter the basic nitrogen overall controls such as the methylamine containing in crude carbinol, dimethylamine in below 20ppm.
It is one-step technology that methanol as above converts gasoline processed, and its reactor adopts heat-insulating fixed bed reactors,
Inlet gas temperature is 300～350 DEG C, and reaction pressure is 1.5～2.5MPa, and methanol quality air speed is 0.8～1.3h-1.
The catalyst that methanol as above converts gasoline processed adopts Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences to develop
JX6201 type catalyst or rope company of Top exploitation GSK-10 type catalyst.
As mentioned above from the gas of methanol separator and the volume of gas phase crude carbinol in the inlet gas of synthesis oil reactor
Than for 4.4～7.8.
The mass ratio of first strand of material as above and second strand of material is 1.5～2.5, wherein passes through artificial oil used heat
The part middle pressure steam that the middle pressure steam that boiler produces is produced with reburner waste heat boiler is used for methanol gasifying after mixing.
Oil gas water separator top as above expellant gas after compression, the gas of wherein volume fraction 3～5%
The fuel gas isolated with oil product separator is sent to after mixing in burning preheating furnace and burns, and remaining gas is back to synthesis gas
Compressor bank.
The present invention compared with prior art, has substantive distinguishing features and marked improvement is：
(1) present invention firstly provides coke-stove gas is through the oily thinking of methanol-fueled CLC, not only for the comprehensive utilization of coke-stove gas
Provide technical strategies, and further increase the economic worth of coke-stove gas, be computed present invention exploitation
Compared with single coke-stove gas methanol, its annual return improves nearly 20% to technology.
(2) coke-stove gas disclosed by the invention is according to coke-stove gas composition characteristic itself, first through methanol-fueled CLC oil technique
Alcohol synthesis and methanol convert many-sided monoblock type technique developed such as gasoline processed, turn with single coke-stove gas methanol and methanol
Change technique for preparing gasoline to compare, the present invention only is routed directly to synthesize oil reactor by the crude carbinol of gas-liquid separation, decreases first
Alcohol rectification cell, its equipment investment decreases more than 10%, and operating cost reduces nearly 5%.
(3) coke-stove gas disclosed by the invention passes through many experiments through methanol-fueled CLC oil technique, simulation calculates and for many years
Experience in design draws, material coupling and Btu utilization all consider from overall technique, it is to avoid single coke-stove gas system
Methanol heat is remaining to waste the contradiction converting gasoline shortage of heat processed with single methanol.
Brief description
Fig. 1 is a kind of flow chart through methanol-fueled CLC oil integrated artistic for the coke-stove gas disclosed by the invention
As illustrated, 1 is burning preheating furnace, 2 is coke oven gas converter, and 3 is gas-liquid separator, and 4 is desulfurizer, and 5 is to close
Become air compressor group, 6 is methanol synthesis reactor, and 7 is evaporative type cooler, and 8 is methanol separator, and 9 is methanol filter, 10
It is flash tank, 11 is synthesis oil reactor, and 12 is oil product air cooler, and 13 is oil gas water separator, and 14 is oil product separator, and 15 are
Recycle gas compressor, 16 is reburner waste heat boiler, and 17 is coke oven air preheater, and 18 is conversion Gas Cooler, and 19 is that methanol closes
Become air preheater, 20 is artificial oil waste heat boiler, and 21 is methanol superheater, and 22 is methanol preheater, 23 methyl alcohol vaporizing devices, and 24 are
Oil product cooler, 25 is artificial oil Reactor inlet air preheater.
Specific embodiment
Below by specific embodiment, the specific embodiment of the present invention is described in further detail, but should be by
This is interpreted as that the scope of the present invention is only limitted to above-described embodiment.
Embodiment 1
(1) volume after purified consists of H260%th, CO 5.3%, CO22.7%th, CH423.7%th, N24.6% and CnHm
3.7% coke-stove gas first allocates a certain amount of supersaturated vapor into, and control supersaturated vapor with the volume ratio of coke-stove gas is
0.25, then worked off one's feeling vent one's spleen heat exchange by coke oven air preheater 17 and coke oven gas converter 2, after through burning preheating furnace 1 further plus
Heat enters in coke oven gas converter 2 to after 600 DEG C, and the oxygen in space division system allocates the supersaturation of 3 times of oxygen volumes into
After steam, enter in converting coke oven gas stove combustor from top, control coke-stove gas to be 4.5 with the volume ratio of oxygen, oxygen
First carry out combustion reaction with coke-stove gas, then gaseous mixture enters catalyst layer from top to bottom and carries out turning under pressure is for 2.5MPa
Change reaction, Z205 catalyst volume fraction is 15% to catalyst layer at the middle and upper levels, and the volume fraction of lower floor's Z204 catalyst is 85%,
After conversion, gas first inverted stove waste heat boiler 16 from after the discharge of bottom reclaims heat, then through coke-stove gas preheater 17 and coke oven
Coal gas heat exchange, then enters in gas-liquid separator 3, fresh water (FW) is discharged from separator bottom after converting Gas Cooler 18 cooling
And after mixing, it is sent to reburner waste heat boiler 16 by-product middle pressure steam with the fresh water (FW) from oil gas water separator, and gas phase is from top
Portion discharges and after the further desulfurization of sulfur protector 4, is mixed into synthesis with the circulating air of 5 times of inverting oven coke furnace gases of volume
Air compressor group 5, in intensified rear entrance methanol synthesis reactor 6.
(2) synthesis gas after supercharging is become air preheater 19 to be worked off one's feeling vent one's spleen with methanol reactor with circulation oxygen mixture ECDC and changes
After heat, from the methanol synthesis reactor that top enters equipped with the C307 catalyst of Research Institute of Nanjing Chemical Industry Group exploitation, in reaction pressure
Power is 5.7MPa, reaction temperature is 240 DEG C and air speed carries out methanol synthesis reaction under conditions of 15500L/ (Kg h), reaction
First through synthesis air preheater 19 and import synthesis gas heat exchange after the exclusion of gas autoreactor bottom colder through evaporative type cooler 7
Enter after solidifying in methanol separator 8, gas phase discharge from separator top and with volume integral after the gas mixing of flash tank 10
The gas of number 71.4% is back to synthesic gas compressor group 5, and 28.6% gas is first through synthesizing oil reactor import air preheater
It is mixed in synthesis oil reactor 11 with the crude carbinol after gasification after 25 preheatings, and by groups such as methanol, fusel, water and lower carbon number hydrocarbons
The crude carbinol liquid phase becoming enters in methanol filter 9 from after the discharge of methanol separator 8 bottom, through be filled with CT151 type acid from
Sub-exchange resin filters and the fatty amine in crude carbinol is removed to after below 0.5ppm, and entrance flash tank 10 carries out flash distillation and divides
From a small amount of gas phase is discharged from flash tank 10 top and mixed with methanol separator 8 tower overhead gas, and crude carbinol liquid phase is from flash tank 10 bottom
Portion enters artificial oil system after discharging.
(3) first preheat through methanol preheater 22 from the crude carbinol of flash tank 10, then gasified, by methyl alcohol vaporizing device 23
By methanol superheater 21 overheated after, with from methanol separator 8 top come gas with volume ratio for 1:4.4 are mixed into dress
Have in the synthesis oil reactor 11 of GSK-10 type catalyst, control inlet gas temperature to be 300 DEG C, and be 2.5MPa in reaction pressure
It is 0.8h with methanol quality air speed-1Under conditions of carry out artificial oil reaction, synthesis oil product is divided into two strands of materials, wherein accounts for synthesis
First strand of material of the 60wt% of oil product total amount is through synthesis oil inlet gas heat exchanger 25 and the gas from methanol separator 8
Enter in oil product air cooler 12 after heat exchange, and the second of 40wt% strand of material first reclaims heat through artificial oil waste heat boiler 20, then
Through methanol superheater 21 and crude carbinol steam heat-exchanging, after change with the liquid phase crude carbinol from filter 10 through methanol preheater 22
It is combined in oil product air cooler 12 with first strand after heat, the synthesis oil product after merging passes through oil product air cooler 12 He further
Enter after oil product cooler 24 cooling in oil gas water separator 13, gas phase is discharged and through recycle gas compressor from separator 13 top
After 15 superchargings, the gas of volume fraction 97% is back to synthesic gas compressor group 5 as circulating air, and remaining 3% gas with
The fuel gas mixing that oil product separator 14 is isolated is sent in burning preheating furnace 1 and is burnt, and the fresh water (FW) of condensation is discharged simultaneously from bottom
With mix from gas-liquid separator 8 fresh water (FW) after be sent to byproduct steam in reburner waste heat boiler 16, and the oil phase isolated enters
Enter in oil product separator 14, obtain fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products after multiple stage separation.In this reality
Apply the artificial oil product form of preparation under the technique of example and reaction condition for details see attached table 1.
Embodiment 2
(1) volume after purified consists of H259.6%th, CO 5.0%, CO23.0%th, CH425.8%th, N23.0% He
CnHm3.6% coke-stove gas first allocates a certain amount of supersaturated vapor into, controls the volume ratio of supersaturated vapor and coke-stove gas
For 0.23, then worked off one's feeling vent one's spleen heat exchange by coke oven air preheater 17 and coke oven gas converter 2, after further through burning preheating furnace 1
Enter in coke oven gas converter 2 after being heated to 620 DEG C, the oxygen in space division system allocates the mistake of 3.1 times of oxygen volumes into
After saturated vapor, enter in converting coke oven gas stove combustor from top, control coke-stove gas to be 4.7 with the volume ratio of oxygen,
And controlling the middle pressure steam allocated into be 0.6 with the volume ratio of coke-stove gas and oxygen, it is anti-that oxygen first carries out burning with coke-stove gas
Should, then gaseous mixture enters catalyst layer from top to bottom and carries out conversion reaction under pressure is for 2.4MPa, and catalyst layer is at the middle and upper levels
Z205 catalyst volume fraction is 18%, and the volume fraction of lower floor's Z204 catalyst is 82%, and after conversion, gas is discharged from bottom
First inverted stove waste heat boiler 16 reclaims heat afterwards, then through coke-stove gas preheater 17 and coke-stove gas heat exchange, then passes through to turn
Activating QI cooler 18 cooling after enter gas-liquid separator 3 in, fresh water (FW) from separator bottom discharge and with from oil and gas and water from
It is sent to reburner waste heat boiler 16 by-product middle pressure steam after the fresh water (FW) mixing of device, and gas phase is discharged and through sulfur protector from top
After 4 further desulfurization, it is mixed into synthesic gas compressor group 5 with the circulating air of 5.2 times of inverting oven coke furnace gases of volume, through increasing
Enter in methanol synthesis reactor 6 after pressure.
(2) synthesis gas after supercharging is become air preheater 19 to be worked off one's feeling vent one's spleen with methanol reactor with circulation oxygen mixture ECDC and changes
After heat, from the methanol synthesis reactor that top enters equipped with the C306 catalyst of Research Institute of Nanjing Chemical Industry Group exploitation, in reaction pressure
Power is 5.8MPa, reaction temperature is 245 DEG C and air speed carries out methanol synthesis reaction under conditions of 16000L/ (Kg h), reaction
First through synthesis air preheater 19 and import synthesis gas heat exchange after the exclusion of gas autoreactor bottom colder through evaporative type cooler 7
Enter after solidifying in methanol separator 8, gas phase discharge from separator top and with volume integral after the gas mixing of flash tank 10
The gas of number 72% is back to synthesic gas compressor group 5, and 28% gas is first pre- through synthesis oil reactor import air preheater 25
It is mixed in synthesis oil reactor 11 with the crude carbinol after gasification after heat, and be made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Crude carbinol liquid phase enters in methanol filter 9 from after the discharge of methanol separator 8 bottom, hands over through being filled with CT151 type acid ion
Change resin filter and the fatty amine in crude carbinol is removed to after below 0.5ppm, enter flash tank 10 and carry out flash separation, few
Amount gas phase is discharged from flash tank 10 top and is mixed with methanol separator 8 tower overhead gas, and crude carbinol liquid phase is arranged from flash tank 10 bottom
Artificial oil system is entered after going out.
(3) first preheat through methanol preheater 22 from the crude carbinol of flash tank 10, then gasified, by methyl alcohol vaporizing device 23
By methanol superheater 21 overheated after, with from methanol separator 8 top come gas with volume ratio for 1:5 be mixed into equipped with
In the synthesis oil reactor 11 of GSK-10 type catalyst, control inlet gas temperature to be 310 DEG C, and reaction pressure for 2.2MPa and
Methanol quality air speed is 0.9h-1Under conditions of carry out artificial oil reaction, synthesis oil product is divided into two strands of materials, wherein accounts for artificial oil
First strand of material of the 62wt% of product population is changed with the gas from methanol separator 8 through synthesis oil inlet gas heat exchanger 25
Enter in oil product air cooler 12 after heat, and the second of 38wt% strand of material first reclaims heat, then warp through artificial oil waste heat boiler 20
Methanol superheater 21 and crude carbinol steam heat-exchanging, after through methanol preheater 22 and the liquid phase crude carbinol heat exchange from filter 10
It is combined in oil product air cooler 12 with first strand afterwards, the synthesis oil product after merging passes through oil product air cooler 12 and oil further
Enter after product cooler 24 cooling in oil gas water separator 13, gas phase is discharged and through recycle gas compressor 15 from separator 13 top
After supercharging, the gas of volume fraction 96% is back to synthesic gas compressor group 5 as circulating air, and remaining 4% gas and oil
The mixing of fuel gas that product separator 14 is isolated is sent in burning preheating furnace 1 and is burnt, the fresh water (FW) of condensation discharge from bottom and with
It is sent to byproduct steam in reburner waste heat boiler 16 after the mixing of gas-liquid separator 8 fresh water (FW), the oil phase isolated enters oil
In product separator 14, obtain fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products after multiple stage separation.
The artificial oil product form for details see attached table 1 of preparation under the technique of the present embodiment and reaction condition.
Embodiment 3
(1) volume after purified consists of H257.8%th, CO 5.7%, CO22.6%th, CH424.2%th, N25.8% He
CnHm3.9% coke-stove gas first allocates a certain amount of supersaturated vapor into, controls the volume ratio of supersaturated vapor and coke-stove gas
For 0.22, then worked off one's feeling vent one's spleen heat exchange by coke oven air preheater 17 and coke oven gas converter 2, after further through burning preheating furnace 1
Enter in coke oven gas converter 2 after being heated to 630 DEG C, the oxygen in space division system allocates the mistake of 3.2 times of oxygen volumes into
After saturated vapor, enter in converting coke oven gas stove combustor from top, control coke-stove gas to be 4.9 with the volume ratio of oxygen,
And controlling the middle pressure steam allocated into be 0.7 with the volume ratio of coke-stove gas and oxygen, it is anti-that oxygen first carries out burning with coke-stove gas
Should, then gaseous mixture enters catalyst layer from top to bottom and carries out conversion reaction under pressure is for 2.3MPa, and catalyst layer is at the middle and upper levels
Z205 catalyst volume fraction is 20%, and the volume fraction of lower floor's Z204 catalyst is 80%, and after conversion, gas is discharged from bottom
First inverted stove waste heat boiler 16 reclaims heat afterwards, then through coke-stove gas preheater 17 and coke-stove gas heat exchange, then passes through to turn
Activating QI cooler 18 cooling after enter gas-liquid separator 3 in, fresh water (FW) from separator bottom discharge and with from oil and gas and water from
It is sent to reburner waste heat boiler 16 by-product middle pressure steam, gas phase is discharged and through sulfur protector 4 from top after the fresh water (FW) mixing of device
Further after desulfurization, it is mixed into synthesic gas compressor group 5 with the circulating air of 5.3 times of inverting oven coke furnace gases of volume, supercharging
Enter afterwards in methanol synthesis reactor 6.
(2) synthesis gas after supercharging is become air preheater 19 to be worked off one's feeling vent one's spleen with methanol reactor with circulation oxygen mixture ECDC and changes
After heat, from the methanol synthesis reactor that top enters equipped with the C307 catalyst of Research Institute of Nanjing Chemical Industry Group exploitation, in reaction pressure
Power is 6.0MPa, reaction temperature is 248 DEG C and air speed carries out methanol synthesis reaction under conditions of 17000L/ (Kg h), reaction
First through synthesis air preheater 19 and import synthesis gas heat exchange after the exclusion of gas autoreactor bottom colder through evaporative type cooler 7
Enter after solidifying in methanol separator 8, gas phase discharge from separator top and with volume integral after the gas mixing of flash tank 10
The gas of number 73% is back to synthesic gas compressor group 5, and 27% gas is first pre- through synthesis oil reactor import air preheater 25
It is mixed in synthesis oil reactor 11 with the crude carbinol after gasification after heat, and be made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Crude carbinol liquid phase enters in methanol filter 9 from after the discharge of methanol separator 8 bottom, hands over through being filled with CT151 type acid ion
Change resin filter and the fatty amine in crude carbinol is removed to after below 0.5ppm, enter flash tank 10 and carry out flash separation, few
Amount gas phase is discharged from flash tank 10 top and is mixed with methanol separator 8 tower overhead gas, and crude carbinol liquid phase is arranged from flash tank 10 bottom
Artificial oil system is entered after going out.
(3) first preheat through methanol preheater 22 from the crude carbinol of flash tank 10, then gasified, by methyl alcohol vaporizing device 23
By methanol superheater 21 overheated after, with from methanol separator 8 top come gas with volume ratio for 1:5.5 are mixed into dress
Have in the synthesis oil reactor 11 of GSK-10 type catalyst, control inlet gas temperature to be 320 DEG C, and be 2.0MPa in reaction pressure
It is 1.0h with methanol quality air speed-1Under conditions of carry out artificial oil reaction, synthesis oil product is divided into two strands of materials, wherein accounts for synthesis
First strand of material of the 64wt% of oil product total amount is through synthesis oil inlet gas heat exchanger 25 and the gas from methanol separator 8
Enter in oil product air cooler 12 after heat exchange, and the second of 36wt% strand of material first reclaims heat through artificial oil waste heat boiler 20, then
Through methanol superheater 21 and crude carbinol steam heat-exchanging, after change with the liquid phase crude carbinol from filter 10 through methanol preheater 22
It is combined in oil product air cooler 12 with first strand after heat, the synthesis oil product after merging passes through oil product air cooler 12 He further
Enter after oil product cooler 24 cooling in oil gas water separator 13, gas phase is discharged and through recycle gas compressor from separator 13 top
After 15 superchargings, the gas of volume fraction 95% is back to synthesic gas compressor group 5 as circulating air, and remaining 5% gas with
The fuel gas mixing that oil product separator 14 is isolated is sent in burning preheating furnace 1 and is burnt, and the fresh water (FW) of condensation is discharged simultaneously from bottom
With mix from gas-liquid separator 8 fresh water (FW) after be sent to byproduct steam in reburner waste heat boiler 16, the oil phase isolated enters
In oil product separator 14, obtain fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products after multiple stage separation.In this enforcement
The artificial oil product form for details see attached table 1 of preparation under the technique of example and reaction condition.
Embodiment 4
(1) volume after purified consists of H254.7%th, CO 6.9%, CO23.5%th, CH425.6%th, N26.1% He
CnHm3.2% coke-stove gas first allocates a certain amount of supersaturated vapor into, controls the volume ratio of supersaturated vapor and coke-stove gas
For 0.20, then worked off one's feeling vent one's spleen heat exchange by coke oven air preheater 17 and coke oven gas converter 2, after further through burning preheating furnace 1
Enter in coke oven gas converter 2 after being heated to 650 DEG C, the oxygen in space division system allocates the mistake of 3.3 times of oxygen volumes into
After saturated vapor, enter in converting coke oven gas stove combustor from top, control coke-stove gas to be 5.0 with the volume ratio of oxygen,
And controlling the middle pressure steam allocated into be 0.8 with the volume ratio of coke-stove gas and oxygen, it is anti-that oxygen first carries out burning with coke-stove gas
Should, then gaseous mixture enters catalyst layer from top to bottom and carries out conversion reaction under pressure is for 2.2MPa, and catalyst layer is at the middle and upper levels
Z205 catalyst volume fraction is 22%, and the volume fraction of lower floor's Z204 catalyst is 78%, and after conversion, gas is discharged from bottom
First inverted stove waste heat boiler 16 reclaims heat afterwards, then through coke-stove gas preheater 17 and coke-stove gas heat exchange, then passes through to turn
Activating QI cooler 18 cooling after enter gas-liquid separator 3 in, fresh water (FW) from separator bottom discharge and with from oil and gas and water from
It is sent to reburner waste heat boiler 16 by-product middle pressure steam after the fresh water (FW) mixing of device, and gas phase is discharged and through sulfur protector from top
After 4 further desulfurization, it is mixed into synthesic gas compressor group 5 with the circulating air of 5.5 times of inverting oven coke furnace gases of volume, through increasing
Enter in methanol synthesis reactor 6 after pressure.
(2) synthesis gas after supercharging is become air preheater 19 to be worked off one's feeling vent one's spleen with methanol reactor with circulation oxygen mixture ECDC and changes
After heat, from the methanol synthesis reactor that top enters equipped with the C302 catalyst of southwestern chemical design institute exploitation, in reaction pressure
Power is 6.2MPa, reaction temperature is 250 DEG C and air speed carries out methanol synthesis reaction under conditions of 18000L/ (Kg h), reaction
First through synthesis air preheater 19 and import synthesis gas heat exchange after the exclusion of gas autoreactor bottom colder through evaporative type cooler 7
Enter after solidifying in methanol separator 8, gas phase discharge from separator top and with volume integral after the gas mixing of flash tank 10
The gas of number 74% is back to synthesic gas compressor group 5, and 26% gas is first pre- through synthesis oil reactor import air preheater 25
It is mixed in synthesis oil reactor 11 with the crude carbinol after gasification after heat, and be made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Crude carbinol liquid phase enters in methanol filter 9 from after the discharge of methanol separator 8 bottom, hands over through being filled with CT151 type acid ion
Change resin filter and the fatty amine in crude carbinol is removed to after below 0.5ppm, enter flash tank 10 and carry out flash separation, few
Amount gas phase is discharged from flash tank 10 top and is mixed with methanol separator 8 tower overhead gas, and crude carbinol liquid phase is arranged from flash tank 10 bottom
Artificial oil system is entered after going out.
(3) first preheat through methanol preheater 22 from the crude carbinol of flash tank 10, then gasified, by methyl alcohol vaporizing device 23
By methanol superheater 21 overheated after, with from methanol separator 8 top come gas with volume ratio for 1:6.0 are mixed into dress
Have in the synthesis oil reactor 11 of JX6201 type catalyst, control inlet gas temperature to be 330 DEG C, and be 1.8MPa in reaction pressure
It is 1.1h with methanol quality air speed-1Under conditions of carry out artificial oil reaction, synthesis oil product is divided into two strands of materials, wherein accounts for synthesis
First strand of material of the 66wt% of oil product total amount is through synthesis oil inlet gas heat exchanger 25 and the gas from methanol separator 8
Enter in oil product air cooler 12 after heat exchange, and the second of 34wt% strand of material first reclaims heat through artificial oil waste heat boiler 20, then
Through methanol superheater 21 and crude carbinol steam heat-exchanging, after change with the liquid phase crude carbinol from filter 10 through methanol preheater 22
It is combined in oil product air cooler 12 with first strand after heat, the synthesis oil product after merging passes through oil product air cooler 12 He further
Enter after oil product cooler 24 cooling in oil gas water separator 13, gas phase is discharged and through recycle gas compressor from separator 13 top
After 15 superchargings, the gas of volume fraction 95% is back to synthesic gas compressor group as circulating air, and remaining 5% gas and oil
The mixing of fuel gas that product separator is isolated is sent in burning preheating furnace 1 and is burnt, the fresh water (FW) of condensation discharge from bottom and with come
It is sent to byproduct steam in reburner waste heat boiler 16 from after the mixing of gas-liquid separator 8 fresh water (FW), and the oil phase isolated enters oil
In product separator 14, obtain fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products after multiple stage separation.
The artificial oil product form for details see attached table 1 of preparation under the technique of the present embodiment and reaction condition.
Embodiment 5
(1) volume after purified consists of H250%th, CO 8%, CO24%th, CH427%th, N27% and CnHm4% Jiao
Producer gas first allocates a certain amount of supersaturated vapor into, controls supersaturated vapor to be 0.19 with the volume ratio of coke-stove gas, then passes through
Coke oven air preheater 17 and coke oven gas converter 2 are worked off one's feeling vent one's spleen heat exchange, after be further heated to after 670 DEG C through burning preheating furnace 1
Enter in coke oven gas converter 2, allocate into after the supersaturated vapor of 3.4 times of oxygen volumes from the oxygen in space division system, from
Top enters and controls the volume ratio of coke-stove gas and oxygen to be 5.2 in converting coke oven gas stove combustor, and controls and allocate into
The volume ratio of pressure steam and coke-stove gas and oxygen is 0.9, and oxygen first carries out combustion reaction with coke-stove gas, then gaseous mixture from
Upper and lower entrance catalyst layer carries out conversion reaction under pressure is for 2.1MPa, catalyst layer Z205 caltalyst integration at the middle and upper levels
Number is 23%, and the volume fraction of lower floor's Z204 catalyst is 77%, gas first inverted stove used heat from after the discharge of bottom after conversion
Boiler 16 reclaims heat, then through coke-stove gas preheater 17 and coke-stove gas heat exchange, then passes through conversion Gas Cooler 18 and cool down
Enter afterwards in gas-liquid separator 3, fresh water (FW) is discharged and after being mixed with the fresh water (FW) from oil gas water separator from separator bottom
It is sent to reburner waste heat boiler 16 by-product middle pressure steam, and gas phase is discharged and after the further desulfurization of sulfur protector 4 from top, with
The circulating air of the inverting oven coke furnace gas of 5.7 times of volume is mixed into synthesic gas compressor group 5, intensified rear entrance methanol-fueled CLC
In reactor 6.
(2) synthesis gas after supercharging is become air preheater 19 to be worked off one's feeling vent one's spleen with methanol reactor with circulation oxygen mixture ECDC and changes
After heat, from the methanol synthesis reactor that top enters equipped with the C302 catalyst of southwestern chemical design institute exploitation, in reaction pressure
Power is 6.3MPa, reaction temperature is 253 DEG C and air speed carries out methanol synthesis reaction under conditions of 19000L/ (Kg h), reaction
First through synthesis air preheater 19 and import synthesis gas heat exchange after the exclusion of gas autoreactor bottom colder through evaporative type cooler 7
Enter after solidifying in methanol separator 8, gas phase discharge from separator top and with volume integral after the gas mixing of flash tank 10
The gas of number 75% is back to synthesic gas compressor group 5, and 25% gas is first pre- through synthesis oil reactor import air preheater 25
It is mixed in synthesis oil reactor 11 with the crude carbinol after gasification after heat, and be made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Crude carbinol liquid phase enters in methanol filter 9 from after the discharge of methanol separator 8 bottom, hands over through being filled with CT151 type acid ion
Change resin filter and the fatty amine in crude carbinol is removed to after below 0.5ppm, enter flash tank 10 and carry out flash separation, few
Amount gas phase is discharged from flash tank 10 top and is mixed with methanol separator 8 tower overhead gas, and crude carbinol liquid phase is arranged from flash tank 10 bottom
Artificial oil system is entered after going out.
(3) first preheat through methanol preheater 22 from the crude carbinol of flash tank 10, then gasified, by methyl alcohol vaporizing device 23
By methanol superheater 21 overheated after, with from methanol separator 8 top come gas with volume ratio for 1:6.5 are mixed into dress
Have in the synthesis oil reactor 11 of JX6201 type catalyst, control inlet gas temperature to be 340 DEG C, and be 1.7MPa in reaction pressure
It is 1.2h with methanol quality air speed-1Under conditions of carry out artificial oil reaction, synthesis oil product is divided into two strands of materials, wherein accounts for synthesis
First strand of material of the 68wt% of oil product total amount is through synthesis oil inlet gas heat exchanger 25 and the gas from methanol separator 8
Enter in oil product air cooler 12 after heat exchange, and the second of 32wt% strand of material first reclaims heat through artificial oil waste heat boiler 20, then
Through methanol superheater 21 and crude carbinol steam heat-exchanging, after change with the liquid phase crude carbinol from filter 10 through methanol preheater 22
It is combined in oil product air cooler 12 with first strand after heat, the synthesis oil product after merging passes through oil product air cooler 12 He further
Enter after oil product cooler 24 cooling in oil gas water separator 13, gas phase is discharged and through recycle gas compressor from separator 13 top
After 15 superchargings, the gas of volume fraction 96% is back to synthesic gas compressor group as circulating air, and remaining 4% gas and oil
The mixing of fuel gas that product separator is isolated is sent in burning preheating furnace 1 and is burnt, the fresh water (FW) of condensation discharge from bottom and with come
It is sent to byproduct steam in reburner waste heat boiler 16 from after the mixing of gas-liquid separator 8 fresh water (FW), and the oil phase isolated enters oil
In product separator 14, obtain fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products after multiple stage separation.
The artificial oil product form for details see attached table 1 of preparation under the technique of the present embodiment and reaction condition.
Embodiment 6
(1) volume after purified consists of H256.2%th, CO 6.4%, CO23.4%th, CH425.1%th, N25.7% He
CnHm3.2% coke-stove gas first allocates a certain amount of supersaturated vapor into, and control saturated vapor with the volume ratio of coke-stove gas is
0.17, then worked off one's feeling vent one's spleen heat exchange by coke oven air preheater 17 and coke oven gas converter 2, after through burning preheating furnace 1 further plus
Heat enters in coke oven gas converter 2 to after 680 DEG C, and the oxygen in space division system allocates the satiety of 3.5 times of oxygen volumes into
After steam, enter in converting coke oven gas stove combustor from top, control coke-stove gas to be 5.3 with the volume ratio of oxygen, and
The middle pressure steam allocated into is controlled to be 0.8 with the volume ratio of coke-stove gas and oxygen, oxygen first carries out combustion reaction with coke-stove gas,
Then gaseous mixture enters catalyst layer from top to bottom and carries out conversion reaction under pressure is for 2.0MPa, catalyst layer Z205 at the middle and upper levels
Catalyst volume fraction is 24%, and the volume fraction of lower floor's Z204 catalyst is 76%, and after conversion, gas is first from after the discharge of bottom
Inverted stove waste heat boiler 16 reclaims heat, then through coke-stove gas preheater 17 and coke-stove gas heat exchange, then passes through to convert gas
Cooler 18 cooling after enter gas-liquid separator 3 in, fresh water (FW) from separator bottom discharge and with from oil gas water separator
It is sent to reburner waste heat boiler 16 by-product middle pressure steam after fresh water (FW) mixing, and gas phase is discharged from top and entered through sulfur protector 4
After one-step desulfurization, it is mixed into synthesic gas compressor group 5 with the circulating air of 5.8 times of inverting oven coke furnace gases of volume, intensified
Enter afterwards in methanol synthesis reactor 6.
(2) synthesis gas after supercharging is become air preheater 19 to be worked off one's feeling vent one's spleen with methanol reactor with circulation oxygen mixture ECDC and changes
After heat, from the methanol synthesis reactor that top enters equipped with the C302 catalyst of southwestern chemical design institute exploitation, in reaction pressure
Power is 6.4MPa, reaction temperature is 256 DEG C and air speed carries out methanol synthesis reaction under conditions of 20000L/ (Kg h), reaction
First through synthesis air preheater 19 and import synthesis gas heat exchange after the exclusion of gas autoreactor bottom colder through evaporative type cooler 7
Enter after solidifying in methanol separator 8, gas phase discharge from separator top and with volume integral after the gas mixing of flash tank 10
The gas of number 74% is back to synthesic gas compressor group 5, and 26% gas is first pre- through synthesis oil reactor import air preheater 25
It is mixed in synthesis oil reactor 11 with the crude carbinol after gasification after heat, and be made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Crude carbinol liquid phase enters in methanol filter 9 from after the discharge of methanol separator 8 bottom, hands over through being filled with CT151 type acid ion
Change resin filter and the fatty amine in crude carbinol is removed to after below 0.5ppm, enter flash tank 10 and carry out flash separation, few
Amount gas phase is discharged from flash tank 10 top and is mixed with methanol separator 8 tower overhead gas, and crude carbinol liquid phase is arranged from flash tank 10 bottom
Artificial oil system is entered after going out.
(3) first preheat through methanol preheater 22 from the crude carbinol of flash tank 10, then gasified, by methyl alcohol vaporizing device 23
By methanol superheater 21 overheated after, with from methanol separator 8 top come gas with volume ratio for 1:7.0 are mixed into dress
Have in the synthesis oil reactor 11 of JX6201 type catalyst, control inlet gas temperature to be 345 DEG C, and be 1.6MPa in reaction pressure
It is 1.3h with methanol quality air speed-1Under conditions of carry out artificial oil reaction, synthesis oil product is divided into two strands of materials, wherein accounts for synthesis
First strand of material of the 70wt% of oil product total amount is through synthesis oil inlet gas heat exchanger 25 and the gas from methanol separator 8
Enter in oil product air cooler 12 after heat exchange, and the second of 30wt% strand of material first reclaims heat through artificial oil waste heat boiler 20, then
Through methanol superheater 21 and crude carbinol steam heat-exchanging, after change with the liquid phase crude carbinol from filter 10 through methanol preheater 22
It is combined in oil product air cooler 12 with first strand after heat, the synthesis oil product after merging passes through oil product air cooler 12 He further
Enter after oil product cooler 24 cooling in oil gas water separator 13, gas phase is discharged and through recycle gas compressor from separator 13 top
After 15 superchargings, the gas of volume fraction 96% is back to synthesic gas compressor group as circulating air, and remaining 4% gas and oil
The mixing of fuel gas that product separator 14 is isolated is sent in burning preheating furnace 1 and is burnt, the fresh water (FW) of condensation discharge from bottom and with
It is sent to byproduct steam in reburner waste heat boiler 16 after the mixing of gas-liquid separator 8 fresh water (FW), the oil phase isolated enters oil
In product separator 14, obtain fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products after multiple stage separation.
The artificial oil product form for details see attached table 1 of preparation under the technique of the present embodiment and reaction condition.
Embodiment 7
(1) volume after purified consists of H260%th, CO 6.0%, CO21.5%th, CH423.3%th, N26.6% and CnHm
2.6% coke-stove gas first allocates a certain amount of supersaturated vapor into, controls saturated vapor to be 0.15 with the volume ratio of coke-stove gas,
Pass through coke oven air preheater 17 and coke oven gas converter 2 again to work off one's feeling vent one's spleen heat exchange, after be further heated to through burning preheating furnace 1
Enter after 700 DEG C in coke oven gas converter 2, the supersaturation that the oxygen in space division system allocates 3.5 times of oxygen volumes into is steamed
After vapour, enter in converting coke oven gas stove combustor from top, control coke-stove gas to be 5.5 with the volume ratio of oxygen, and control
The middle pressure steam allocated into is 0.9 with the volume ratio of coke-stove gas and oxygen, and oxygen first carries out combustion reaction, then with coke-stove gas
Gaseous mixture enters catalyst layer from top to bottom and carries out conversion reaction under pressure is for 2.3MPa, catalyst layer Z205 catalysis at the middle and upper levels
Agent volume fraction is 25%, and the volume fraction of lower floor's Z204 catalyst is 75%, and after conversion, gas first warp from after the discharge of bottom turns
Change stove waste heat boiler 16 and reclaim heat, then through coke-stove gas preheater 17 and coke-stove gas heat exchange, then pass through to convert air cooling
Device 18 cooling after enter gas-liquid separator 3 in, fresh water (FW) from separator bottom discharge and with the technique from oil gas water separator
It is sent to reburner waste heat boiler 16 by-product middle pressure steam after water mixing, and gas phase is discharged and further through sulfur protector 4 from top
After desulfurization, it is mixed into synthesic gas compressor group 5 with the circulating air of 6.0 times of inverting oven coke furnace gases of volume, enter after supercharging
In methanol synthesis reactor 6.
(2) synthesis gas after supercharging is become air preheater 19 to be worked off one's feeling vent one's spleen with methanol reactor with circulation oxygen mixture ECDC and changes
After heat, from the methanol synthesis reactor that top enters equipped with the RK-5 type catalyst of Dalian Reak Science and Technology Co., Ltd.'s exploitation,
Reaction pressure be 6.5MPa, reaction temperature be to carry out methanol-fueled CLC under conditions of 260 DEG C and air speed are 18000L/ (Kg h)
Reaction, first through synthesis air preheater 19 and import synthesis gas heat exchange after the exclusion of reacting gas autoreactor bottom, then through vaporation-type
Cooler 7 condensation after enter methanol separator 8 in, gas phase from separator top discharge and with the gas mixing from flash tank 10
The gas of volume fraction 75% is back to synthesic gas compressor group 5 afterwards, and 25% gas is first pre- through synthesis oil reactor inlet gas
It is mixed in synthesis oil reactor 11 with the crude carbinol after gasification after hot device 25 preheating, and by methanol, fusel, water and lower carbon number hydrocarbons
Crude carbinol liquid phase Deng composition enters in methanol filter 9 from after the discharge of methanol separator 8 bottom, through being filled with the acid of CT151 type
Property ion exchange resin filter and the fatty amine in crude carbinol is removed to after below 0.5ppm, enter flash tank 10 carry out flash distillation
Separate, a small amount of gas phase is discharged from flash tank 10 top and mixed with methanol separator 8 tower overhead gas, and crude carbinol liquid phase is from flash tank 10
Bottom enters artificial oil system after discharging.
(3) first preheat through methanol preheater 22 from the crude carbinol of flash tank 10, then gasified, by methyl alcohol vaporizing device 23
By methanol superheater 21 overheated after, with from methanol separator 8 top come gas with volume ratio for 1:7.1 are mixed into dress
Have in the synthesis oil reactor 11 of JX6201 type catalyst, control inlet gas temperature to be 350 DEG C, and be 1.5MPa in reaction pressure
It is 1.2h with methanol quality air speed-1Under conditions of carry out artificial oil reaction, synthesis oil product is divided into two strands of materials, wherein accounts for synthesis
First strand of material of the 70wt% of oil product total amount is through synthesis oil inlet gas heat exchanger 25 and the gas from methanol separator 8
Enter in oil product air cooler 12 after heat exchange, and the second of 30wt% strand of material first reclaims heat through artificial oil waste heat boiler 20, then
Through methanol superheater 21 and crude carbinol steam heat-exchanging, after change with the liquid phase crude carbinol from filter 10 through methanol preheater 22
It is combined in oil product air cooler 12 with first strand after heat, the synthesis oil product after merging passes through oil product air cooler 12 He further
Enter after oil product cooler 24 cooling in oil gas water separator 13, gas phase is discharged and through recycle gas compressor from separator 13 top
After 15 superchargings, the gas of volume fraction 96% is back to synthesic gas compressor group as circulating air, and remaining 4% gas and oil
The mixing of fuel gas that product separator is isolated is sent in burning preheating furnace 1 and is burnt, the fresh water (FW) of condensation discharge from bottom and with come
It is sent to byproduct steam in reburner waste heat boiler 16 from after the mixing of gas-liquid separator 8 fresh water (FW), and the oil phase isolated enters oil
In product separator 14, obtain fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products after multiple stage separation.
Under the technique of the present embodiment and reaction condition, the artificial oil product form of preparation refers to table 1.
Table 1
Claims (15)
1. a kind of technique through methanol synthesized gasoline for coke-stove gas is it is characterised in that comprise the steps：Comprise the steps：
(1) coke-stove gas after purified first allocates supersaturated vapor into, then is gone out by coke oven air preheater and coke oven gas converter
Implication heat exchange, after heat further through burning preheating furnace after enter in coke oven gas converter, oxygen in space division system
After allocating supersaturated vapor into, enter in coke oven gas converter combustor from top and first carry out combustion reaction with coke-stove gas, then
Gaseous mixture after burning enters from top to bottom in coke oven gas converter catalyst layer and carries out conversion reaction, and after conversion, gas is from bottom
After discharge, first inverted stove waste heat boiler reclaims heat, then through coke oven air preheater and coke-stove gas heat exchange, then passes through conversion
Enter after Gas Cooler cooling in gas-liquid separator, separate the fresh water (FW) that obtains discharge from gas-liquid separator bottom and with from oil
It is sent to reburner waste heat boiler by-product middle pressure steam, a part of middle pressure steam of by-product enters after the fresh water (FW) mixing of moisture trap
After the preheating furnace that enters to burn forms supersaturated vapor after being heated, respectively with purify after coke-stove gas and in the space division system
Oxygen mix enters the top of coke oven gas converter, and another part middle pressure steam provides heat of vaporization for methyl alcohol vaporizing device, separates
The gas phase arriving is discharged from gas-liquid separator, and is mixed into synthesic gas compressor group with circulating air after the further desulfurization of desulfurizer
In be pressurized；
(2) after the reacting gas heat exchange through synthesis air preheater and the discharge of methanol reactor bottom for the mixed gas after being pressurized, from
Top enters in methanol synthesis reactor and carries out methanol synthesis reaction, and reacting gas is discharged from methanol synthesis reactor bottom, first
Through synthesizing air preheater heat exchange, then enter in methanol separator after evaporative type cooler condensation, gas phase is from methanol separator top
Portion discharges and is back to synthesic gas compressor group with the gas mixing rear portion gas from flash tank, and another part gas is first
It is mixed in synthesis oil reactor with the crude carbinol after gasification after synthesis oil reactor import air preheater preheating, and by first
Alcohol, the crude carbinol liquid phase of fusel, water and lower carbon number hydrocarbons composition enter in methanol filter, through acid from after the discharge of methanol separator bottom
Property ion exchange resin filter after enter flash tank carry out flash separation, a small amount of gas phase from flash tank top discharge and separating methanol
Device tower overhead gas mixes, and crude carbinol liquid phase is discharged from flash drum bottom；
(3) crude carbinol coming from flash tank is first through methanol preheater preheating, then gasified by methyl alcohol vaporizing device, after through methanol mistake
After hot device is overheated, enters in synthesis oil reactor with the gas mixing from artificial oil Reactor inlet air preheater and synthesized
Oil reaction, synthesis oil product is divided into two strands of materials, and wherein first strand material divides with from methanol through synthesis oil inlet gas heat exchanger
Enter in oil product air cooler after the gas converting heat that device comes, and second strand of material first reclaims heat through artificial oil waste heat boiler, then
Through methanol superheater and crude carbinol steam heat-exchanging, after through methanol preheater with from the liquid phase crude carbinol heat exchange of filter after with
First strand of material merges, and the synthesis oil product after merging enters oil further after oil product air cooler and the cooling of oil product cooler
In moisture trap, gas phase is discharged and after recycle gas compressor supercharging from oil gas water separator top, a part of gas conduct
Circulating air is back to synthesic gas compressor group, the fuel gas that another part is isolated with oil product separator mix being sent to burning preheating
Burn in stove, the fresh water (FW) condensing out is discharged from oil gas water separator bottom and mixed with the fresh water (FW) from gas-liquid separator
After be sent to byproduct steam in reburner waste heat boiler, and the oil phase isolated enters in oil product separator, obtains fuel after separating
Air-liquid liquefied oil gas, heavy oil and gasoline products.
2. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that purified and de-
After sulfur, the volume of coke-stove gas consists of H250～60%, CO 5%～8%, CO21.5～4%, CH423%～27%, N2
3～7%, C2Above unsaturated hydrocarbons 2～4%.
3. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that oven gas conversion
Stove is fixed bed adiabatic reactor, and its reaction pressure is 2.0～2.5MPa, and coke-stove gas inlet temperature is 600～700oC, turns
Change stove and be divided into top combustor and bottom conversion chamber, bottom conversion chamber loads upper and lower two-layer catalyst, upper strata converts for Z205 type
Catalyst, its admission space accounts for 15～25Vol% of beds cumulative volume；Lower floor is Z204 type reforming catalyst, filling
Volume accounts for 75～85Vol% of beds cumulative volume.
4. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that entering oven gas
The coke-stove gas of reburner and the volume ratio of oxygen are 4.5～5.5.
5. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that reburner used heat
It is partly into burning preheating furnace in the middle pressure steam that boiler produces and produces supersaturated vapor, supersaturated vapor passes through to allocate into respectively
Coke-stove gas is back in reburner with the mode allocating oxygen into, and wherein control supersaturated vapor with the volume ratio of coke-stove gas is
0.15～0.25, control supersaturated vapor to be 3.0～3.5 with the volume ratio of oxygen, remaining another part middle pressure steam is sent to
Methyl alcohol vaporizing device is used for methanol gasifying.
6. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described methanol
Synthesis reactor adopts shell-and-tube temperature reactor, and its reaction pressure is 5.7～6.5MPa, and reaction temperature is 240～260 DEG C, gas
Body air speed is 15500～20000L/Kg h.
7. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described methanol
C306, C307 catalyst that the catalyst of synthesis is developed for Research Institute of Nanjing Chemical Industry Group, or the C302 of southwestern chemical design institute exploitation
One of catalyst.
8. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described entrance
The circulating air sum from methanol separator and oil gas water separator in synthesic gas compressor group with from desulfurizer gas phase
Volume ratio is 5.0～6.0.
9. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described methanol
The gas phase that separator top is discharged with merge from the gas phase that flash tank is discharged after for two parts, be wherein back to synthesis gas and compress
The gas of unit with enter the gas volume ratio of methanol synthesis reactor for 2.5～3.0.
10. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described methanol
The CT151 type acid-exchange resin that in filter, filling Piao Laite company produces, the first containing in crude carbinol after filtering
Amine, dimethylamine basic nitrogen overall control are in below 20ppm.
11. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described synthesis
Oil reacts for one-step technology, and its reactor adopts heat-insulating fixed bed reactors, and inlet gas temperature is 300～350 DEG C, reaction
Pressure is 1.5～2.5MPa, and methanol quality air speed is 0.8～1.3h-1.
12. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described synthesis
The catalyst of oil reaction adopts the GSK-10 type catalyst of rope company of Top exploitation.
13. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described artificial oil
The volume ratio of the gas and gas phase crude carbinol that are derived from methanol separator in the inlet gas of reactor is 4.4～7.8.
14. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described first
The mass ratio of stock material and second strand of material is 1.5～2.5, the middle pressure steam wherein producing by artificial oil waste heat boiler and turn
It is used for methanol gasifying after changing the part middle pressure steam mixing that stove waste heat boiler produces.
15. as claimed in claim 1 a kind of technique through methanol synthesized gasoline for coke-stove gas it is characterised in that described oil gas
Water separator top expellant gas after compression, the combustion that wherein gas of volume fraction 3～5% is isolated with oil product separator
It is sent in burning preheating furnace after material gas mixing and burns, and remaining gas is back to synthesic gas compressor group.
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| CN105419849A (en) * | 2015-11-09 | 2016-03-23 | 赛鼎工程有限公司 | Energy-saving type technology for manufacturing gasoline by converting methanol |
| CN106349017B (en) * | 2016-08-30 | 2018-10-26 | 安徽金禾实业股份有限公司 | A kind of recovery method of refined methanol processing tail gas |
| CN107964415A (en) * | 2016-10-19 | 2018-04-27 | 深圳市新路田科技有限公司 | A kind of method and system of coupling between methanol liquefied petroleum gas gasoline |
| CN107964417A (en) * | 2016-10-19 | 2018-04-27 | 深圳市新路田科技有限公司 | A kind of method and system of preparing gasoline by methanol |
| CN107964414A (en) * | 2016-10-19 | 2018-04-27 | 深圳市新路田科技有限公司 | A kind of method and system of coupling between methanol liquefied petroleum gas lightweight low-coagulation diesel oil |
| CN107964416A (en) * | 2016-10-19 | 2018-04-27 | 深圳市新路田科技有限公司 | A kind of method and system of coupling between methanol light naphtha gasoline |
| CN107964418A (en) * | 2016-10-19 | 2018-04-27 | 深圳市新路田科技有限公司 | A kind of method and system of methanol lightweight low-coagulation diesel oil |
| CN108854167B (en) * | 2018-09-17 | 2023-12-05 | 陕西黑猫焦化股份有限公司 | Recycling system of condensate after methane steam conversion in coke oven gas |
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| DE3805397A1 (en) * | 1988-02-20 | 1989-08-24 | Ruhrkohle Ag | Process for producing fuel methanol (motor fuel) from coke oven gas and metallurgical plant gas |
| US6248794B1 (en) * | 1999-08-05 | 2001-06-19 | Atlantic Richfield Company | Integrated process for converting hydrocarbon gas to liquids |
| CN100471825C (en) * | 2006-09-15 | 2009-03-25 | 中国科学院山西煤炭化学研究所 | Technology of preparing hydrocarbons produce from methanol by one-step method |
| CN101244805B (en) * | 2008-03-13 | 2010-10-06 | 四川天一科技股份有限公司 | Method for producing methanol synthesis gas by oven gas non-catalytic pure oxygen-steam conversion |
| CN101538483B (en) * | 2009-04-03 | 2013-04-17 | 中国科学院山西煤炭化学研究所 | Poly-generation technique for using coal gas and coke oven gas as raw materials |
| MX2015003867A (en) * | 2012-10-23 | 2015-07-17 | Haldor Topsøe As | Process for the preparation of hydrocarbons. |
| CN104557371B (en) * | 2014-12-12 | 2016-02-24 | 赛鼎工程有限公司 | A kind of fixed bed adiabatic reactor single stage method methanol conversion produces the method for hydrocarbon mixture |
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