CN103820140A - Process for preparing gasoline through synthesis gas - Google Patents
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- CN103820140A CN103820140A CN201410079811.5A CN201410079811A CN103820140A CN 103820140 A CN103820140 A CN 103820140A CN 201410079811 A CN201410079811 A CN 201410079811A CN 103820140 A CN103820140 A CN 103820140A
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Abstract
A process for preparing gasoline through synthesis gas is characterized in that pressurized synthesis gas is sent into a slurry bed reactor loaded with a catalyzer for synthesizing dimethyl ether to synthesize dimethyl ether, gas coming from the slurry bed reactor directly enters into a fixed bed reactor loaded with a catalyzer for synthesizing gasoline to synthesize gasoline, one part of mixed gas coming from the fixed bed reactor enters into a gas-liquid separator after being preheated for synthesizing gas through a heat exchanger, the rest part of the mixed gas enters into the gas-liquid separator after the heat of the rest part is recycled through an exhaust boiler, then liquid phase and gas are obtained after separation, the liquid phase comprises gasoline and water, one part of gas is discharged or used for other purposes, and the other part of gas circulates and returns to the slurry bed reactor through a compressor. The process provided by the invention has the advantages that the conversion per pass of the synthesis gas is high, energy consumption is low, the cost is low, and the service life of the catalyzer is long.
Description
Technical field
The invention belongs to a kind of synthetic gas process of gasoline processed, relate in particular to a kind of technique of starching state bed-fixed bed coupling gasoline processed.
Background technology
The few oil of the rich coal of China, expects the year two thousand twenty, and the external interdependency of China's oil likely approaches 65%, and therefore, development substitute energy source for petroleum is extremely urgent, and coal liquefaction becomes the important trend of China's energy strategy.
At present, coal oil-producing technique mainly comprises direct liquefaction technique and the indirect liquefaction technique of coal.The processing condition of the direct liquefaction of coal are very harsh, and product complexity is not easily separated; The indirect liquefaction technology of coal is first coal gas to be changed into synthetic gas, then, take coal based synthetic gas (carbon monoxide and hydrogen) as raw material, under certain temperature and pressure, is catalyzed and synthesized the technique into hydrocarbon fuel oil and industrial chemicals.At present, ICL for Indirect Coal Liquefaction technology mainly comprises two kinds of Fischer-Tropsch synthesis method and synthesis gas through methanol gasoline methods processed.The synthetic product complexity making of Fischer-Tropsch, light weight fluid hydrocarbon is few, generally also needs hydrotreatment, invests too large; And synthesis gas through methanol gasoline method processed can directed synthetic gasoline, aromatic hydrocarbons, alkene, and the gasoline knock resistance that this method makes is good, do not have the component such as sulphur, chlorine in conventional gasoline, and chemical constitution is very similar to conventional gasoline, has good prospects for commercial application.In patent (CN101519336A), introduced a kind of technique of producing hydrocarbon with synthetic gas, this technique is mainly made up of synthesising gas systeming carbinol and methanol dewatered hydro carbons two portions.In this patent, synthesising gas systeming carbinol adopts fixed bed, but because methyl alcohol building-up reactions (1) belongs to strong exothermal reaction, in reaction process, catalyzer is inactivation under hot conditions very easily, need a large amount of circulating cooling mediums, and must limit synthetic gas transformation efficiency, can not produce too much heat because transformation efficiency is too high and make sintering of catalyst inactivation, therefore, this process energy consumption is high, and product yield is low.Methanol dehydration comprises that two-step reaction (2) and (3) are all strong exothermal reactions, and in reaction process, catalyzer is high-temperature coking inactivation very easily, and catalyst life is shortened, and does not meet industrialized production requirement.
CO+2H
2→CH
3OH+102.5kJ (1)
CH
3OH→1/2(CH
3)
2O+1/2H
2O+10.1kJ (2)
1/2(CH
3)
2O→‐CH
2‐+1/2H
2O+34.7kJ (3)
Summary of the invention
The per pass conversion that the object of this invention is to provide a kind of synthetic gas is high, and energy consumption is low, and cost is low, the technique of the synthetic gas gasoline processed of catalyst life length.
From synthetic gas gasoline reaction processed (1), (2), (3), institute responds and is thermopositive reaction, for reaching above-mentioned purpose, the present invention adopts slurry state bed single stage method synthetic gas preparing dimethy ether, utilize slurry state bed bed temperature advantage even, easy control of reaction system can greatly improve the per pass conversion of CO, and then avoid sintering of catalyst and inactivation, reduce the internal circulating load of synthetic gas, avoid the use of circulating cooling liquid, simultaneously, the raw material of gasoline synthesis phase is become to dme, thereby can reduce subordinate phase liberated heat, and can improve the life-span of catalyzer.
Processing step of the present invention is as follows:
Pressurization synthetic gas is by sending into dimethyl ether synthesis in the paste state bed reactor that synthesizing dimethyl ether catalyst is housed, directly enter synthetic gasoline the fixed-bed reactor that Synthetic gasoline catalyst is housed from paste state bed reactor gas out, from a fixed-bed reactor mixed gas part out by the pre-hot synthesis gas of interchanger laggard enter gas-liquid separator, remainder enters gas-liquid separator after waste heat boiler reclaims heat, after separation, obtain liquid phase and gas, liquid phase is gasoline and water, a part gas emptying or its use, another part gas is by compressor cycle overfall state bed reactor.
Dimethyl ether catalyst as above adopts dual-function catalyst, as the dual-function catalyst LP201+TH16(LP201 mass content 67% of Tsing-Hua University's exploitation, TH16 mass content 33%), the composition of this catalyzer of dual-function catalyst CN1176742C(of Nan Hua group exploitation mainly comprises metal oxide and acidic components, wherein suitable metal oxide weight content: CuO is 20%-40%, ZnO is 15%-30%, and acidic components are γ-Al that pseudobochmite roasting makes
2o
3, its weight percentage is 25%-85%), the synthesis condition of dme is synthetic gas hydrogen carbon volume ratio 1-4, and temperature of reaction is at 220-300 ℃, and reaction pressure is at 0.5-8MPa, and air speed is at 1000-8000mlg
-1h
-1.
The synthesis condition of dme as above is more excellent is synthetic gas hydrogen carbon volume ratio 2-3, temperature of reaction 230-250 ℃, reaction pressure 2-4MPa, air speed 3000-6000mlg
-1h
-1.
Adopt slurry state bed single stage method synthetic gas preparing dimethy ether, require the performance of catalyzer can reach CO per pass conversion > 60%, H
2per pass conversion > 40%, synthetic dme further reacts generation gasoline.Solved key issue---the low conversion rate of CO in synthetic gas gasoline processed, when having improved CO transformation efficiency, being unlikely to make to react liberated heat affects the catalytic performance of catalyzer.
The ZSM-5 catalyzer that Synthetic gasoline catalyst as above adopts modification to prepare, is specially several as follows:
1, the ZSM-5 catalyzer that prepared by soda acid modification
(1) the HCl solution that is 1-4mol/L by concentration, under 50-80 ℃ of condition, processing silica alumina ratio is the business H-ZSM-5 molecular sieve 10min-300min of 25-100, centrifugal after dilute acid soln washing, at 450-600 ℃, roasting 3-5h, obtains ZSM-5/H
+molecular sieve;
(2) the NaOH solution that is 0.1-1mol/L by concentration is processed ZSM-5/H under 50-80 ℃ of condition
+molecular sieve 10min-300min, centrifugal after dilute acid soln washing, roasting 3-5h at 450-600 ℃ ℃, obtains ZSM-5/OH-molecular sieve;
(3) NH that is 0.2-0.8mol/L by concentration
4nO
3solution carries out ion-exchange to ZSM-5/OH-molecular sieve, obtains modification H-ZSM-5 molecular sieve.
2, the ZSM-5 catalyzer of soda acid and metal-modified preparation
(1) the HCl solution that is 1-4mol/L by concentration, under 50-80 ℃ of condition, processing silica alumina ratio is the business H-ZSM-5 molecular sieve 10min-300min of 25-100, centrifugal after dilute acid soln washing, at 450-600 ℃, roasting 3-5h, obtains ZSM-5/H
+molecular sieve;
(2) the NaOH solution that is 0.1-1mol/L by concentration is processed ZSM-5/H under 50-80 ℃ of condition
+molecular sieve 10min-300min, centrifugal after dilute acid soln washing, roasting 3-5h at 450-600 ℃ ℃, obtains ZSM-5/OH-molecular sieve;
(3) NH that is 0.2-0.8mol/L by concentration
4nO
3solution carries out ion-exchange, obtains H-ZSM-5 molecular sieve;
(4) H-ZSM-5 molecular sieve is carried out to the salts solution of incipient impregnation M metal, the mass content 1-10% of M metal, obtains M/H-ZSM-5 molecular sieve, and wherein M metal is Cu, Co or Mn.
The reaction conditions of synthetic gasoline is: temperature of reaction 340-450 ℃, reaction pressure 0.5-5MPa, air speed 0.8-5h
-1.
The reaction conditions of synthetic gasoline as above is more excellent is temperature of reaction 360-420 ℃, reaction pressure 1-4MPa, air speed 1-3h
-1.
The present invention adopts dme gasoline processed, dimethyl ether conversion rate 100%, and liquid hydrocarbon's recovery ratio > 90%, the gasoline obtaining meets the Europe IV standard.
The present invention compared with prior art, will starch state bed and introduce synthetic gas gasoline process processed, solve the fixed bed difficult difficult problem of dispelling the heat.Use separately fixed bed synthesising gas systeming carbinol or dme, then further synthetic gasoline, the per pass conversion of CO must not exceed 10%, otherwise the amount of heat that reaction produces raises reactor temperature, the selectivity trend low-carbon (LC) hydro carbons that makes on the one hand product, yield of gasoline declines; Make on the other hand sintering of catalyst inactivation, be unfavorable for the stability of catalyzer.But in order to reach higher CO transformation efficiency, can use many still series connection or use in a large number circulating cooling medium, but corresponding facility investment increases greatly.To starch state bed introduces after synthetic gas gasoline process processed, the per pass conversion of CO rises to 60%, solve the problem that CO low conversion rate, circulation of tail gas amount in fixed bed are used circulating cooling medium greatly, in a large number, realized the Efficient Conversion to gasoline by synthetic gas simultaneously, simplified technical process.The present invention compared with the prior art, in the transformation efficiency that has improved synthetic gas, do not affect the catalytic activity of catalyzer, energy consumption and cost are reduced, utilize the high-temperature gas producing in fixed bed that high pressure steam is provided, as public thermal source, improved the utilization ratio of energy, the present invention has also extended the life-span of catalyzer to a great extent.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention
As shown in Figure 1,1 synthetic gas, 2 interchanger, synthetic gas after 3 preheatings, 4 paste state bed reactors, tail gas after 5 slurry reactors, 6 fixed-bed reactor, 7,9 control valves, the tail gas of 8 pre-hot synthesis gas, 10 waste heat boilers, 11 enter the tail gas of gas-liquid separator, 12 gas-liquid separators, the circulation gas of 13 circulation overfall state beds, 14 emptying or he with gas, 15 compressors, 16 liquid products
Embodiment
Below in conjunction with accompanying drawing 1, by specific embodiment, the present invention is described in detail, but be also not only confined to embodiment.
Embodiment 1
Step (1) synthetic gas 1, is mainly to be made by gasification of coal or Sweet natural gas cracking, and hydrogen carbon volume ratio is 2, is pressurized to 2.5MPa, through interchanger 2 heat exchange, enters paste state bed reactor 4 with the tail gas 8 of pre-hot synthesis gas after preheating.
Step (2) paste state bed reactor 2 adopts air-flow bubbling suspension paste state bed reactor, and adopting whiteruss is inertia liquid phase thermal barrier, 240 ℃ of temperature of reaction, reaction pressure 2.5MPa, air speed 6000mlg
-1h
-1, synthetic gas in this reactor through dual-function catalyst (the dual-function catalyst LP201+TH16(LP201 mass content 67% of Tsing-Hua University exploitation, TH16 mass content 33%)) dehydration generates dme, wherein CO per pass conversion 65%.
Tail gas 5 after step (3) slurry reactor directly enters fixed-bed reactor 6, in fixed-bed reactor 6, be equipped with and business ZSM-5 carried out to the catalyzer of modification (it is 50 business H-ZSM-5 molecular sieve 300min that 2mol/L HCl solution is processed silica alumina ratio under 80 ℃ of conditions, the dilute nitric acid solution of 0.5mol/L is centrifugal after washing 5 times, roasting 5h at 550 ℃, and then under 80 ℃ of conditions, process the molecular sieve 120min after acid treatment with 0.4mol/L NaOH solution, the dilute nitric acid solution of 0.5mol/L is centrifugal after washing 5 times, roasting 5h at 550 ℃ ℃, with the NH of 0.2mol/L
4nO
3solion exchange 3 times, each 12h, deionized water wash 5 times, the oven dry of spending the night at 100 ℃, roasting 5h at 550 ℃ ℃, then incipient impregnation Mn (NO
3)
2solution, Mn mass content 5wt%), 380 ℃ of temperature of reaction, reaction pressure 2MPa, air speed 3h
-1, dme is transformation efficiency 100% after catalyzer, liquid hydrocarbon's recovery ratio 92%.
The part mixed gas that step (4) fixed-bed reactor 6 export is controlled by control valve 7, first enter the pre-hot synthesis gas of interchanger 2, then enter gas-liquid separator 12, first rest part gas enter waste heat boiler 10 and reclaim the tail gas 11 that enters gas-liquid separator 12 after heat and then enter gas-liquid separator 12, be not liquefied or unsegregated portion gas through 14 emptying or collect his use, another part loops back the circulation gas 13 of paste state bed reactor 4 through 15 compressor cycle overfall state bed reactors 4.
Step (5), in step (4), through the isolated liquid product 16 of gas-liquid separator 12, after separating, gasoline enters storage tank and collects.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 22%, aromatic hydrocarbons volume fraction content 30%, meets the Europe IV standard.
Embodiment 2
Step (1) synthetic gas 1, is mainly to be made by gasification of coal or Sweet natural gas cracking, and hydrogen carbon volume ratio is 3, is pressurized to 2.0MPa, through interchanger 2 heat exchange, enters paste state bed reactor 4 with the tail gas 8 of pre-hot synthesis gas after preheating.
Step (3), (4), (5) are with embodiment 1
Step (2) paste state bed reactor 4 adopts air-flow bubbling suspension paste state bed reactor, adopt whiteruss be inertia liquid phase thermal barrier, and with normal hexane as supercritical medium, 250 ℃ of temperature of reaction, reaction pressure 3MPa, air speed 5000mlg
-1h
-1, synthetic gas in this reactor through dual-function catalyst (the dual-function catalyst LP201+TH16(LP201 mass content 67% of Tsing-Hua University exploitation, TH16 mass content 33%)) dehydration generates dme, wherein CO per pass conversion 65%, H
2per pass conversion 62%.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 20%, aromatic hydrocarbons volume fraction content 32%, meets the Europe IV standard.
Embodiment 3
Step (1) synthetic gas 1, is mainly to be made by gasification of coal or Sweet natural gas cracking, and hydrogen carbon volume ratio is 2.5, is pressurized to 4.0MPa, through interchanger 2 heat exchange, enters paste state bed reactor 4 with the tail gas 8 of pre-hot synthesis gas after preheating.
Step (3), (4), (5) are with embodiment 1
Step (2) paste state bed reactor 4 adopts mechanical stirring autoclave slurry state bed, and adopting whiteruss is inertia liquid phase thermal barrier, and with normal hexane as supercritical medium, 230 ℃ of temperature of reaction, reaction pressure 4MPa, air speed 3000mlg
-1h
-1synthetic gas in this reactor through dual-function catalyst (the dual-function catalyst CN1176742C of Nan Hua group exploitation, the composition of this catalyzer mainly comprises metal oxide and acidic components, wherein suitable metal oxide weight content: CuO is 30%, ZnO is 20%, and acidic components are γ-Al that pseudobochmite roasting makes
2o
3, its weight percentage is 50%) and dehydration generation dme, wherein CO per pass conversion 70%, H
2per pass conversion 47%.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 18%, aromatic hydrocarbons volume fraction content 30%, meets the Europe IV standard.
Embodiment 4
Step (1), (2), (4), (5) are with embodiment 1
After step (3) slurry reactor, tail gas 5 directly enters fixed-bed reactor 6, in fixed-bed reactor 6, be equipped with and business ZSM-5 carried out to the catalyzer of modification (it is 100 business H-ZSM-5 molecular sieve 100min that 4mol/L HCl solution is processed silica alumina ratio under 60 ℃ of conditions, the dilute nitric acid solution of 0.8mol/L is centrifugal after washing 3 times, roasting 3h at 600 ℃, and then under 50 ℃ of conditions, process the molecular sieve 10min after acid treatment with 1.0mol/L NaOH solution, centrifugal after washing 3 times with the dilute nitric acid solution of 0.8mol/L, roasting 3h at 600 ℃ ℃, with the NH of 0.8mol/L
4nO
3solion exchange 3 times, each 6h, deionized water wash 5 times, the oven dry of spending the night at 110 ℃, roasting 4h at 500 ℃ ℃, then incipient impregnation Co (NO
3)
2solution, Co mass content 10wt%), 400 ℃ of temperature of reaction, reaction pressure 3MPa, air speed 1.0h
-1, dme is transformation efficiency 100% after catalyzer, liquid hydrocarbon's recovery ratio 90%.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 20%, aromatic hydrocarbons volume fraction content 33%, meets the Europe IV standard.
Embodiment 5
Step (1), (2), (4), (5) are with embodiment 1
After step (3) slurry reactor, tail gas 5 directly enters fixed-bed reactor 6, in fixed-bed reactor vapour 6, be equipped with and business ZSM-5 carried out to the catalyzer of modification (it is 25 business H-ZSM-5 molecular sieve 10min that 1mol/L HCl solution is processed silica alumina ratio under 50 ℃ of conditions, the dilute nitric acid solution of 0.2mol/L is centrifugal after washing 6 times, roasting 4h at 450 ℃, and then under 70 ℃ of conditions, process the molecular sieve 100min after acid treatment with 0.1mol/L NaOH solution, centrifugal after washing 6 times with the dilute nitric acid solution of 0.2mol/L, roasting 4h at 450 ℃ ℃, with the NH of 0.5mol/L
4nO
3solion exchange 3 times, each 8h, deionized water wash 5 times, the oven dry of spending the night at 120 ℃, roasting 5h at 550 ℃ ℃, then incipient impregnation Cu (NO
3)
2solution, Cu mass content 1wt%), 420 ℃ of temperature of reaction, reaction pressure 4MPa, air speed 3.0h
-1, dme is transformation efficiency 100% after catalyzer, liquid hydrocarbon's recovery ratio 90%.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 23%, aromatic hydrocarbons volume fraction content 33%, meets the Europe IV standard.
Step (1), (2), (4), (5) are with embodiment 1
After step (3) slurry reactor, tail gas 5 directly enters fixed-bed reactor 6, in fixed-bed reactor 6, be equipped with and ZSM-5 carried out to the catalyzer of modification (it is 60 business H-ZSM-5 molecular sieve 300min that 1.5mol/L HCl solution is processed silica alumina ratio under 80 ℃ of conditions, the dilute nitric acid solution of 0.3mol/L is centrifugal after washing 5 times, roasting 5h at 550 ℃, and then under 80 ℃ of conditions, process the molecular sieve 80min after acid treatment with 0.6mol/L NaOH solution, the dilute nitric acid solution of 0.5mol/L is centrifugal after washing 5 times, roasting 5h at 550 ℃ ℃, with the NH of 0.5mol/L
4nO
3solion exchange 3 times, each 8h, deionized water wash 5 times, the oven dry of spending the night at 120 ℃, roasting 5h at 550 ℃ ℃), 360 ℃ of temperature of reaction, reaction pressure 1.0MPa, air speed 1.8h
-1, dme is transformation efficiency 100% after catalyzer, liquid hydrocarbon's recovery ratio 94%.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 23%, aromatic hydrocarbons volume fraction content 29%, meets the Europe IV standard.
Embodiment 7
Step (1), (2), (4), (5) are with embodiment 1
After step (3) slurry reactor, tail gas 5 directly enters fixed-bed reactor 6, in fixed-bed reactor 6, be equipped with and ZSM-5 carried out to the catalyzer of modification (it is 40 business H-ZSM-5 molecular sieve 200min that 3mol/L HCl solution is processed silica alumina ratio under 80 ℃ of conditions, the dilute nitric acid solution of 1.0mol/L is centrifugal after washing 5 times, roasting 4h at 600 ℃, and then under 80 ℃ of conditions, process the molecular sieve 80min after acid treatment with 0.2mol/L NaOH solution, the dilute nitric acid solution of 1.0mol/L is centrifugal after washing 5 times, roasting 4h at 600 ℃ ℃, with the NH of 0.3mol/L
4nO
3solion exchange 3 times, each 8h, deionized water wash 5 times, the oven dry of spending the night at 120 ℃, roasting 5h at 550 ℃ ℃), 390 ℃ of temperature of reaction, reaction pressure 1.5MPa, air speed 2.5h
-1, dme is transformation efficiency 100% after catalyzer, liquid hydrocarbon's recovery ratio 91%.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 24%, aromatic hydrocarbons volume fraction content 30%, meets the Europe IV standard.
Step (1), (2), (4), (5) are with embodiment 1
After step (3) slurry reactor, tail gas 5 directly enters fixed-bed reactor 6, in fixed-bed reactor 6, be equipped with and ZSM-5 carried out to the catalyzer of modification (it is 80 business H-ZSM-5 molecular sieve 300min that 2.5mol/L HCl solution is processed silica alumina ratio under 80 ℃ of conditions, the dilute nitric acid solution of 1.2mol/L is centrifugal after washing 5 times, roasting 5h at 550 ℃, and then under 80 ℃ of conditions, process the molecular sieve 90min after acid treatment with 0.3mol/L NaOH solution, the dilute nitric acid solution of 1.2mol/L is centrifugal after washing 5 times, roasting 5h at 550 ℃ ℃, with the NH of 0.8mol/L
4nO
3solion exchange 3 times, each 8h, deionized water wash 5 times, the oven dry of spending the night at 110 ℃, roasting 5h at 550 ℃ ℃, then incipient impregnation Mn (NO
3)
2solution, Mn mass content 8wt%), 410 ℃ of temperature of reaction, reaction pressure 2.0MPa, air speed 1.5h
-1, dme is transformation efficiency 100% after catalyzer, liquid hydrocarbon's recovery ratio 91%.
Unleaded in the gasoline obtaining, iron, manganese, sulphur, volume fraction of olefins content 24%, aromatic hydrocarbons volume fraction content 30%, meets the Europe IV standard.
Claims (10)
1. a technique for synthetic gas gasoline processed, is characterized in that comprising the steps:
Pressurization synthetic gas is by sending into dimethyl ether synthesis in the paste state bed reactor that synthesizing dimethyl ether catalyst is housed, directly enter synthetic gasoline the fixed-bed reactor that Synthetic gasoline catalyst is housed from paste state bed reactor gas out, from a fixed-bed reactor mixed gas part out by the pre-hot synthesis gas of interchanger laggard enter gas-liquid separator, remainder enters gas-liquid separator after waste heat boiler reclaims heat, after separation, obtain liquid phase and gas, liquid phase is gasoline and water, a part gas emptying or its use, another part gas is by compressor cycle overfall state bed reactor.
2. the technique of a kind of synthetic gas as claimed in claim 1 gasoline processed, is characterized in that described dimethyl ether catalyst adopts the LP201 of Tsing-Hua University's exploitation and the dual-function catalyst of TH16 composition; The dual-function catalyst of Nan Hua group exploitation, the composition of this catalyzer mainly comprises metal oxide and acidic components, and metal oxide weight content: CuO is 20%-40%, and ZnO is 15%-30%, and acidic components are γ-Al that pseudobochmite roasting makes
2o
3, its weight percentage is 25%-85%.
3. the technique of a kind of synthetic gas as claimed in claim 2 gasoline processed, is characterized in that consisting of of dual-function catalyst that described LP201 and TH16 form: LP201 mass content 67%, TH16 mass content 33%.
4. the technique of a kind of synthetic gas as claimed in claim 1 gasoline processed, is characterized in that the synthesis condition of described dme is synthetic gas hydrogen carbon volume ratio 1-4, and temperature of reaction is at 220-300 ℃, and reaction pressure is at 0.5-8MPa, and air speed is at 1000-8000mlg
-1h
-1.
5. the technique of a kind of synthetic gas as claimed in claim 4 gasoline processed, is characterized in that the synthesis condition of described dme is synthetic gas hydrogen carbon volume ratio 2-3, temperature of reaction 230-250 ℃, reaction pressure 2-4MPa, air speed 3000-6000mlg
-1h
-1.
6. the technique of a kind of synthetic gas as claimed in claim 1 gasoline processed, is characterized in that the ZSM-5 catalyzer that described Synthetic gasoline catalyst adopts modification to prepare.
7. the technique of a kind of synthetic gas as claimed in claim 6 gasoline processed, is characterized in that ZSM-5 catalyzer prepared by described modification prepared by the following method:
(1) the HCl solution that is 1-4mol/L by concentration, under 50-80 ℃ of condition, processing silica alumina ratio is the business H-ZSM-5 molecular sieve 10min-300min of 25-100, centrifugal after dilute acid soln washing, at 450-600 ℃, roasting 3-5h, obtains ZSM-5/H
+molecular sieve;
(2) the NaOH solution that is 0.1-1mol/L by concentration is processed ZSM-5/H under 50-80 ℃ of condition
+molecular sieve 10min-300min, centrifugal after dilute acid soln washing, roasting 3-5h at 450-600 ℃ ℃, obtains ZSM-5/OH
-molecular sieve;
(3) by concentration be the NH of 0.2-0.8 mol/L
4nO
3solution is to ZSM-5/OH
-molecular sieve carries out ion-exchange, obtains modification H-ZSM-5 molecular sieve.
8. the technique of a kind of synthetic gas as claimed in claim 6 gasoline processed, is characterized in that ZSM-5 catalyzer prepared by described modification prepared by the following method:
(1) the HCl solution that is 1-4mol/L by concentration, under 50-80 ℃ of condition, processing silica alumina ratio is the business H-ZSM-5 molecular sieve 10min-300min of 25-100, centrifugal after dilute acid soln washing, at 450-600 ℃, roasting 3-5h, obtains ZSM-5/H
+molecular sieve;
(2) the NaOH solution that is 0.1-1mol/L by concentration is processed ZSM-5/H under 50-80 ℃ of condition
+molecular sieve 10min-300min, centrifugal after dilute acid soln washing, roasting 3-5h at 450-600 ℃ ℃, obtains ZSM-5/OH
-molecular sieve;
(3) by concentration be the NH of 0.2-0.8 mol/L
4nO
3solution carries out ion-exchange, obtains H-ZSM-5 molecular sieve;
(4) H-ZSM-5 molecular sieve is carried out to the salts solution of incipient impregnation M metal, the mass content 1-10% of M metal, obtains M/H-ZSM-5 molecular sieve, and wherein M metal is Cu, Co or Mn.
9. the technique of a kind of synthetic gas as claimed in claim 1 gasoline processed, is characterized in that the reaction conditions of described synthetic gasoline is: temperature of reaction 340-450 ℃, reaction pressure 0.5-5MPa, air speed 0.8-5h
-1.
10. the technique of a kind of synthetic gas as claimed in claim 9 gasoline processed, the reaction conditions that it is characterized in that described synthetic gasoline is temperature of reaction 360-420 ℃, reaction pressure 1-4MPa, air speed 1-3h
-1.
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| CN85100759A (en) * | 1985-04-01 | 1986-09-03 | 中国科学院山西煤炭化学研究所 | Zeolite [molecular sieve and preparation thereof |
| US20040044090A1 (en) * | 2000-10-13 | 2004-03-04 | Font Freide Josephus Johannes Helena Maria | Fischer-tropsch synthesis process |
| CN1463290A (en) * | 2001-05-03 | 2003-12-24 | 俄罗斯科学院阿·弗·托普奇耶娃石油化工合成所 | Method for prodn. of gasoline from gaseous hydrocarbon stock |
| CN103007983A (en) * | 2012-10-08 | 2013-04-03 | 太原理工大学 | HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof |
| CN103433067A (en) * | 2013-09-09 | 2013-12-11 | 中国科学院上海高等研究院 | Catalyst for preparing gasoline from methyl alcohol as well as preparation and application of catalyst |
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