CN1382676A - Process for preparing dimethylether from synthetic gas by reaction on slurry-state bed - Google Patents
Process for preparing dimethylether from synthetic gas by reaction on slurry-state bed Download PDFInfo
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- CN1382676A CN1382676A CN 01134106 CN01134106A CN1382676A CN 1382676 A CN1382676 A CN 1382676A CN 01134106 CN01134106 CN 01134106 CN 01134106 A CN01134106 A CN 01134106A CN 1382676 A CN1382676 A CN 1382676A
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Abstract
A process for preparing dimethylether from synthetic gas with slurry-state bed features choosing inertial solvent, preparing dual-function catalyst, controlling reaction temp (200-350 deg.C), reaction pressure (2-10 MPa), and space speed of synthetic gas (500-5000/hr), and suppressing by-reaction. Its advantages are high conversion rate of CO (up to 72.45%) and high selectivity of dimethylether (up to 95.26%).
Description
Technical field: the invention belongs to the C-1 chemistry technical field, be specifically related to a kind of process for preparing dimethylether from synthetic gas by reaction on slurry-state bed and relevant device thereof.
Background technology: three relatively independent reactions take place preparing dimethylether from synthetic gas by reaction: the reaction of co hydrogenation synthesizing methanol, methanol dehydration generate dme reaction and water gas shift reaction.The liquid composition characteristic of total reaction rate and paste state bed reactor, thermodynamics of reactions, catalyst system, reaction conditions all have relation.The existing people of slurry attitude bed reaction technique is applied to the synthetic gas preparing dimethy ether, and for example U.S. Pat 5218003, US5389689, and US5753716, Japanese Patent JP3-181435, they adopt slurry attitude bed synthetic gas preparing dimethy ether technology.From present research level, can make the synthetic gas per pass conversion reach 30%～50% usually, the dme selectivity reaches 50%～80%.
Summary of the invention: the object of the invention provides and a kind ofly improves per pass conversion and dme optionally process for preparing dimethylether from synthetic gas by reaction on slurry-state bed and equipment by operation conditions optimization.
Process for preparing dimethylether from synthetic gas by reaction on slurry-state bed of the present invention, adopt paste state bed reactor, it is suspended in dual-function catalyst in the inert liquid medium, synthetic gas at first dissolves in inert media, then be diffused into the copper-based catalysts surface and react generation methyl alcohol, further react the generation dme on the methanol dehydration catalyst surface again.Therefore, slurry attitude bed synthetic gas preparing dimethy ether process had both comprised chemical process, comprised physical processes such as dissolving, diffusion, absorption, desorb again.Particularly, develop dual-function catalyst by selecting inert solvent for use, control reaction temperature, reaction pressure, the synthetic gas air speed, it is synthetic to make whole reaction system help dme, reaches the purpose that suppresses side reaction.Above-mentioned inert solvent is whiteruss, mineral oil, aromatic hydrocarbons and derivative thereof.Above-mentioned dual-function catalyst is made up of methanol synthesis catalyst and methanol dehydration catalyst, dual-function catalyst median size 50～300 orders, dual-function catalyst density 0.7～1.5g/cm
3200～300 ℃ of described temperature of reaction, described reaction pressure 3.0～7.0MPa.
Solvent of the present invention, under operation condition, synthetic gas solubleness is higher, does not influence the activity and the selectivity of dual-function catalyst in synthesizing methanol and dme process, and is less with the reaction product mutual solubility, is liquid phase in reaction system.This solvent can be benzene, methyl-phenoxide, biphenyl ether, whiteruss, mineral oil.
The determined dual-function catalyst of the present invention adopts metal-salt and the acid co-precipitation deposition of forming to form, metal oxide is one or more the mixture in cupric oxide, zinc oxide, chromic oxide, the cerium oxide in the catalyzer, acidic components are one or more the mixture in molecular sieve, aluminum oxide, the aluminum phosphate, metal oxide weight percentage in dual-function catalyst is 30%～70%, and acidic components weight percentage in dual-function catalyst is 25%～65%.Acidic components are homemade or commodity pseudobochmite constant temperature calcining under 500～600 ℃ of conditions of temperature is no less than 2h, make γ-Al
2O
3, wherein metal oxide weight CuO is 20%～40%, ZnO is 15%～30%.
The determined range of reaction temperature of the present invention is 200～350 ℃, and optimal reaction temperature is 230～300 ℃, and process for preparing dimethylether from synthetic gas by reaction on slurry-state bed effectively reduces the active temperature of dual-function catalyst dehydration component.If use γ-Al separately
2O
3As the catalyzer of dimethyl ether by methanol dehydration, its active temperature will be more than 290 ℃, and best dehydration activity temperature is 300～350 ℃, when temperature of reaction is 260 ℃, and γ-Al
2O
3The catalytic dehydration activity does not almost have.The invention solves in the dual-function catalyst the unmatched problem of active temperature between synthetic component of methyl alcohol and the methanol dehydration component.
The determined operation pressure range of the present invention is 2.0～10.0MPa, and optimum operation pressure is 3.0～7.0MPa, and the synthetic gas air speed is: 500～5000h
-1
The novel pulpous bed reaction of preparing dimethyl ether technology of the present invention owing to optimized multiple operational condition, has improved CO per pass conversion and dme selectivity effectively.
Description of drawings: accompanying drawing 1 is process flow diagram of the present invention.In the accompanying drawing 1, the R-reactor; The E-interchanger; The F-gas-liquid separator; D-level pressure device; Tank body in the middle of the G-; The C-recycle compressor; The H-primary cooler; T1-takes off the CO2 tower; T2-dme rectifying tower; The T3-methanol rectifying tower.
Embodiment: further specify the present invention below in conjunction with embodiment.
Embodiment one
With granularity 100～200 purpose DME-98 type dual-function catalysts, the reactor of packing into after mixing with whiteruss is used N
2-H
2After the gas mixture reduction, switch to synthetic gas, the synthetic gas volume consists of (H
2/ CO=2.83, CO2 0.64%), be 256 ℃ in temperature of reaction, reaction pressure is 4.0MPa, air speed is 1200h
-1Condition under, the CO transformation efficiency is 67.93%, the dme selectivity is 94.26%.
Embodiment two
With granularity is 100～200 purpose DME-98 type dual-function catalysts, and the reactor of packing into after mixing with whiteruss is used N
2-H
2After the gas mixture reduction, switch to synthetic gas, the synthetic gas volume consists of (H
2/ CO=2.83, CO
20.64%), be 265 ℃ in temperature of reaction, reaction pressure is 4.0MPa, air speed is 1200h
-1Condition under, the CO transformation efficiency is 72.45%, the dme selectivity is 95.26%.
Process for preparing dimethylether from synthetic gas by reaction on slurry-state bed equipment used of the present invention comprises: paste state bed reactor, primary cooler, condensation separator, recycle compressor, CO
2Remove equipment such as device, dme rectifying tower and methanol rectifying tower.The process for preparing dimethylether from synthetic gas by reaction on slurry-state bed flow process is seen accompanying drawing 1, and 1. synthetic gas enters paste state bed reactor R, carries out preparing dimethylether from synthetic gas by reaction with the operational condition of embodiment 2, and the mixture of drawing from reactor head mainly contains not reacted H
2, CO, CO
2, resultant dme, methyl alcohol, water and solvent of carrying secretly out and catalyzer.This mixture is at first at the primary cooler internal cooling, and temperature drops to about 100 ℃, and pressure remains unchanged substantially.Liquid phase is solvent, part methyl alcohol, water and contains the catalyzer of carrying secretly on a small quantity in the primary cooler, and they are Returning reactor under action of gravity; Gas phase mixture carries out gas-liquid separation by gas-liquid separator F after entering watercooler E3 condensation, and gas phase mixture is 6. a part of as tail gas
Emptying, rest part are 7. via after the recycle compressor C supercharging, and is 9. mixed with virgin gas, 1. reenters reactor R as synthetic gas.
10. phlegma enters through level pressure device D1 and interchanger E4 and takes off CO2 tower T1, removes the liquid product behind the CO2, through level pressure device D2, behind middle vessel G1 and the interchanger E6, isolates qualified dme product, remaining fluid by dme rectifying tower T2
Isolate the first alcohol and water by methanol rectifying tower T3.
Claims (5)
1. a reaction process of starching attitude bed synthetic gas preparing dimethy ether is characterized in that reaction process mainly comprises three phase slurry bed bioreactor, primary cooler, condensation separator, recycle compressor, CO2 removal tower, dme rectifying tower and methanol rectifying tower; Introduce inert solvent in the reactor, by control reaction temperature 200-350 ℃, reaction pressure 2.0-10.0MPa, synthetic gas air speed 500-5000h
-1, form gas-liquid-solid three-phase state with synthetic gas, dual-function catalyst; Dual-function catalyst is that copper-based catalysts adds γ-Al
2O
3, its manufacture method can be methanol synthesis catalyst and γ-Al
2O
3Mechanically mixing also can be a precipitation of joint sedimentation, and its quality compositing formula is: CuO 20%-40%, ZnO 15%-30%, Al
2O
325%-65%.
2. the reaction process of a slurry attitude bed synthetic gas preparing dimethy ether as claimed in claim 1 is characterized in that described inert solvent is whiteruss, mineral oil, aromatic hydrocarbons and derivative thereof.
3. the reaction process of a slurry attitude bed synthetic gas preparing dimethy ether as claimed in claim 1 is characterized in that control reaction temperature is 230-300 ℃.
4. the reaction process of a slurry attitude bed synthetic gas preparing dimethy ether as claimed in claim 1, it is characterized in that controlling reaction pressure is 3.0-7.0Mpa.
5. the reaction process of a slurry attitude bed synthetic gas preparing dimethy ether as claimed in claim 1, it is characterized in that controlling the synthetic gas air speed is 1000-1400h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01134106 CN1382676A (en) | 2001-10-30 | 2001-10-30 | Process for preparing dimethylether from synthetic gas by reaction on slurry-state bed |
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|---|---|---|---|
| CN 01134106 CN1382676A (en) | 2001-10-30 | 2001-10-30 | Process for preparing dimethylether from synthetic gas by reaction on slurry-state bed |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314491C (en) * | 2004-09-18 | 2007-05-09 | 太原理工大学 | Catalyst for sizing bed and its preparation |
| CN101130487B (en) * | 2006-08-23 | 2010-06-30 | 中国科学院工程热物理研究所 | Method for landfill of gas fluidification dimethyl ether fuel by garbage |
| CN101372446B (en) * | 2007-08-23 | 2014-05-28 | 赫多特普索化工设备公司 | Process for the preparation of dimethyl ether |
| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
-
2001
- 2001-10-30 CN CN 01134106 patent/CN1382676A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314491C (en) * | 2004-09-18 | 2007-05-09 | 太原理工大学 | Catalyst for sizing bed and its preparation |
| CN101130487B (en) * | 2006-08-23 | 2010-06-30 | 中国科学院工程热物理研究所 | Method for landfill of gas fluidification dimethyl ether fuel by garbage |
| CN101372446B (en) * | 2007-08-23 | 2014-05-28 | 赫多特普索化工设备公司 | Process for the preparation of dimethyl ether |
| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
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