CN1188379C - Process for preparing dimethylether from natural gas via partial oxidation by air or oxygen-enriched air to make gas - Google Patents
Process for preparing dimethylether from natural gas via partial oxidation by air or oxygen-enriched air to make gas Download PDFInfo
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- CN1188379C CN1188379C CNB001102613A CN00110261A CN1188379C CN 1188379 C CN1188379 C CN 1188379C CN B001102613 A CNB001102613 A CN B001102613A CN 00110261 A CN00110261 A CN 00110261A CN 1188379 C CN1188379 C CN 1188379C
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Abstract
The present invention relates to a process for preparing dimethyl ether from natural gas via the partial oxidation of air or oxygen-enriched air, which is characterized in that the natural gas is used as raw material and dimethyl ether is synthesized by two stages of reactions; in the first-stage reaction, the natural gas and the catalytic part of the air or the oxygen-enriched air are oxidized to make synthetic gas containing nitrogen; in the second-stage reaction, synthetic gas containing nitrogen, methane and carbon dioxide is synthesized to dimethyl ether with high conversion rate after water in the resultant of the first-stage reaction is removed. The present invention has the advantages of less investment for equipment and low synthesis cost.
Description
The present invention relates to a kind of technological process by natural gas via air (or oxygen-rich air) partial oxidation gas making preparing dimethy ether, specifically, the present invention is made of two-stage reaction, first section reaction relates to Sweet natural gas and air (or oxygen-rich air) catalyzing part oxidation made synthesis gas containing nitrogen, regulates CO and H in the synthetic gas at needs
2During ratio, also can add an amount of water vapour and (or) carbonic acid gas; Second section reaction is after the product with first section reaction removes water, will contain nitrogen and a small amount of methane and carbonic acid gas the synthetic gas high conversion synthesize dme.
At present, the annual production of world's dme is about 150,000 tons, and mainly the sprays carrier as aerosol industry uses.Since the nineties, having it is found that dme can replace diesel oil and liquefied petroleum gas (LPG) to use well, is 21 century ideal clean fuel, and in addition, dme can also be as the raw material of producing low-carbon alkene.Clearly, when if dme uses as the clean fuel use with as the raw material of producing low-carbon alkene, its unit scale at least should be more than 1,000,000 tons/year, and dme will reach and vapour, diesel oil or the suitable output of ethene when the time comes, become a kind of large Chemicals and industrial chemicals.
At present, methyl alcohol catalytic dehydration technology, its small scale, production cost height are mainly adopted in dme production.The scale operation dme should adopt the direct conversion process of natural gas via synthetic gas.In natural gas via synthetic gas preparing dimethy ether process, the Sweet natural gas synthetic gas production process has decisive role, and its plant investment and production cost account for about 60% of whole dme building-up process.Industrialized at present Sweet natural gas synthetic gas production process is to adopt Sweet natural gas and steam reforming method:
Strong endothermic reaction is not only in this reaction, and is slow reaction, and therefore, this process is the energy consumption height not only, and unit scale and plant investment are big, in addition, and H in the synthetic gas of this prepared in reaction
2/ CO=3/1, synthetic gas is rich in hydrogen, and its composition is unsuitable for doing dme synthetic unstripped gas.
Since the nineties, methane pure oxygen portion oxidation synthesis gas at home and abroad causes pays close attention to (Ashcroft A.T.et al., Nature, 344,319,1990 widely; Ashcroft A.T.et al., Nature, 352,225,1991; Hickman D.A., and Schmidt, L.D., Science, 259,343,1993.).This technological process is compared with industrialized steam reforming method at present, because its grow heat absorption is gentle heat release, thereby has the low obvious advantage of energy consumption, in addition, this reaction can be carried out under very big air speed, also can reduce unit scale and investment.In addition, this reaction can provide H
2The synthetic gas of/CO=2/1, synthetic gas are formed and are suitable for doing dme synthetic unstripped gas.But the shortcoming of methane pure oxygen partial oxidation reaction is, increased expensive air separation plant investment and system oxygen cost when industrial applications, therefore, obviously increased plant investment and unstripped gas cost.
The purpose of this invention is to provide a kind of method by natural gas via air or oxygen-rich air partial oxidation gas making preparing dimethy ether, its required equipment less investment, thereby synthetic with low cost.
The invention provides a kind of method by natural gas via air or oxygen-rich air partial oxidation gas making preparing dimethy ether, it is characterized in that: be that raw material is by the two-stage reaction dimethyl ether synthesis with the Sweet natural gas, first section reaction is that Sweet natural gas and air or oxygen-rich air catalyzing part oxidation are made synthesis gas containing nitrogen, the condition of first section gas making reaction is: 600～960 ℃ of temperature, pressure 0.2～3.0MPa, Sweet natural gas/air when air is raw material=1/1～1/3, when oxygen-rich air is raw material, O in the oxygen-rich air
2/ N
2=1/3.5～1/0.1, Sweet natural gas/oxygen=1/0.2～1/0.7, Sweet natural gas air speed 1000～100000h
-1Second section reaction is after the product with first section reaction removes water, to contain nitrogen, methane and carbonic acid gas the synthetic gas high conversion synthesize dme, the condition of second section dme building-up reactions is: 160 ℃～320 ℃ of temperature, pressure 1.0Mpa～15.0Mpa, unstripped gas air speed 400～10000h
-1
Can add an amount of water vapour and/or carbonic acid gas in first section reaction of the present invention to regulate CO and H in the synthetic gas
2Ratio, when adding water and/or carbonic acid gas, CH
4/ H
2O=0.1～2.0, CH
4/ CO
2=0.1～2.0
First section reacting middle catalyst of the present invention can adopt supported catalyst, active ingredient is selected from one or more in nickel, rhodium, the platinum, wherein the loading of metallic nickel is 2～12wt%, and the loading of metal rhodium is 0.1～2wt%, and the loading of metal platinum is 0.1～2wt%.Above-mentioned catalyzer can also adopt rare earth or mishmetal and/or alkaline-earth metal to modify, and its modification amount is: rare earth metal 0.5～6%, alkaline-earth metal 0.5～5%.
The present invention utilizes one or both or three kinds of metals in nickel, rhodium and the platinum as the catalyst activity component, active constituent loading is made catalyzer on oxide carriers such as aluminum oxide, silicon oxide, be used for Sweet natural gas and air (or oxygen-rich air) are converted into synthetic gas, under pressurized conditions also can to reaction system add a certain amount of water vapour and (or) carbonic acid gas, purpose is to strengthen remaining methane conversion and avoid catalyst carbon deposition, and regulates CO and H in the product
2Ratio; After condensation removed water, other components comprised H with the product of Sweet natural gas air (or oxygen-rich air) partial oxidation preparation
2, CO, CH
4, CO
2, N
2Gas mixture all feed the reactor dimethyl ether synthesis that conventional synthesizing dimethyl ether by synthetic gas catalyzer is housed.Owing to can obtain higher yield with synthesizing dimethyl ether by synthetic gas, reactor feed gas need not circulate in reaction system, thereby nitrogen is less relatively to the influence that consumes compression work.The present invention replaces pure oxygen to carry out gas making with air (or oxygen-rich air) in a word, can avoid expensive air separation plant investment and increase system oxygen cost, thereby can significantly reduce the manufacturing cost of synthetic gas, the synthetic gas of the present invention's preparation contains nitrogen in addition, do not need nitrogen separation is removed, get final product dimethyl ether synthesis, thereby synthetic cost reduces significantly.
The technology of the present invention details is by the detailed description in addition of following example:
Embodiment 1
Take by weighing Ni/Al respectively
2O
3, Rh/Al
2O
3And Pt/Al
2O
3Catalyzer 5g, in the fixed-bed reactor that the stainless steel of packing into is made, catalyzer nickel content is 5%, and Rh content is 0.5%, and Pt content is 0.5%.Catalyzer is through H
2700 ℃ of reduction activation half an hour, the unstripped gas of introducing Sweet natural gas/air/water steam (volume ratio)=1/2.4/0.8 reacts, and reaction pressure is 0.8Mpa, 800 ℃ of temperature of reaction, and gas discharge is 600ml/min.Reaction result sees Table 1.
Table 1 Sweet natural gas, air and steam reforming prepare dme synthetic raw gas reaction result
Catalyzer CH
4CO
2H
2O CO H
2N
2R
Ni/Al
2O
3 1.78 4.17 12.3 12.3 35.3 34.2 1.89
Rh/Al
2O
3 1.69 4.04 12.4 12.6 35.2 34.1 1.87
Pt/Al
2O
3 3.06 4.97 13.0 10.6 33.0 35.4 1.80
R＝(H
2-CO
2)/(CO+CO
2)
Embodiment 2
Take by weighing Rh content and be 0.5% Rh/Al
2O
3Catalyzer 5g, in the fixed-bed reactor that the stainless steel of packing into is made, catalyzer is through H
2700 ℃ of reduction activation half an hour, the unstripped gas of introducing Sweet natural gas/air/water steam (volume ratio)=1/2.0/1.0 reacts, and temperature of reaction is 800 ℃, and gas discharge is 600ml/min, and the reaction result under the different pressures sees Table 2.The result shows that prepared synthetic gas R value is suitable for doing dme synthetic unstripped gas.
Table 2 Sweet natural gas, air and steam reforming prepare dme synthetic raw gas reaction result
Pressure (MPa) CH
4CO
2H
2O CO H
2N
2R
0.1 0.15 4.07 11.2 14.1 42.4 28.1 2.11
0.4 1.11 4.00 12.2 13.5 40.5 28.7 2.09
0.8 2.08 4.36 13.4 12.3 38.7 29.2 2.06
1.0 2.55 4.60 14.1 11.7 37.3 29.7 2.01
R＝(H
2-CO
2)/(CO+CO
2)
Embodiment 3
Take by weighing with La
2O
3Ni-Pt/Al with the MgO modification
2O
3Catalyzer 10g, in the fixed-bed reactor that the stainless steel of packing into is made, catalyzer nickel content is 5%, platinum content is 0.5%, La
2O
3Be respectively 2% and 1.5% with Mg content.Catalyzer is through H
2700 ℃ of reduction activation half an hour, the unstripped gas of introducing Sweet natural gas/oxygen-rich air/water vapour (volume ratio)=1/1.5/1.0 reacts (the oxygen volume content accounts for 30% in the oxygen-rich air), temperature of reaction is 800 ℃, gas discharge is 1200ml/min, and the reaction result under the different pressures sees Table 3.
Table 3 Sweet natural gas, oxygen-rich air and steam reforming preparing dimethy ether synthetic raw gas reaction result
Pressure (MPa) CH
4CO
2H
2O CO H
2N
2R
0.1 0.06 4.42 13.3 15.5 45.8 20.9 2.08
0.4 0.79 4.67 14.2 14.8 44.4 21.2 2.04
0.8 2.34 5.09 15.6 13.3 41.9 21.8 2.00
1.0 3.03 5.24 16.4 12.7 40.5 22.1 1.97
R＝(H
2-CO
2)/(CO+CO
2)
Embodiment 4
Take by weighing Ni/Al with the mixed rare-earth oxide modification
2O
3Catalyzer 10g, in the fixed-bed reactor that the stainless steel of packing into is made, catalyzer nickel content is 5%, mixed rare-earth oxide content and Mg content are respectively 4% and 1.5%.Catalyzer is through H
2700 ℃ of reduction activation half an hour, the unstripped gas of introducing Sweet natural gas, air, water vapour and carbonic acid gas reacts, and temperature of reaction is 800 ℃, and pressure is 0.8Mpa, and gas discharge is 1200ml/min.Water and carbonic acid gas ratio see Table 4 to the influence of reaction result in the unstripped gas.As seen, by the ratio of water and carbonic acid gas in the adjusting unstripped gas, can control the R value of product.
Table 4 Sweet natural gas, air, water vapour and carbonic acid gas transform preparing dimethy ether synthetic raw gas reaction result
Sweet natural gas/air/water steam
CH
4 CO
2 H
2O CO H
2 N
2 R
/ carbonic acid gas
1/2.0/0.0/1.0 1.32 5.32 14.9 15.8 27.6 35.0 1.06
1/2.0/0.2/0.8 1.53 5.04 14.6 15.0 30.1 33.7 1.25
1/2.0/0.5/0.5 1.68 4.84 13.9 13.8 33.8 31.8 1.55
1/2.0/0.8/0.2 2.00 4.57 13.7 12.8 36.7 30.2 1.85
1/2.0/1.0/0.0 2.26 4.31 13.7 12.2 38.3 29.3 2.06
R＝(H
2-CO
2)/(CO+CO
2)
Embodiment 5
Take by weighing with La
2O
3Ni/Al with the MgO modification
2O
3Catalyzer 5g, in the fixed-bed reactor that the stainless steel of packing into is made, catalyzer nickel content is 5%, La
2O
3Be respectively 2% and 1.5% with Mg content.Catalyzer is through H
2700 ℃ of reduction activation half an hour, the unstripped gas of introducing Sweet natural gas/air/water steam (volume ratio)=1/2.0/1.0 reacts, and reaction pressure is 0.8Mpa, 800 ℃ of temperature of reaction, and gas discharge is 600ml/min.The moment reaction result that reacted 200 hours sees Table 5.
Table 5 Sweet natural gas, air and steam reforming prepare dme synthetic raw gas reaction result
Reaction times CH
4CO
2H
2O CO H
2N
2R
5 2.08 4.28 13.5 12.6 38.4 29.2 2.02
50 2.02 4.34 13.6 12.3 38.6 29.2 2.06
100 2.09 4.27 13.4 12.4 38.8 29.1 2.07
150 2.16 4.10 13.2 12.8 38.7 29.1 2.06
200 2.07 4.29 13.4 12.5 38.6 29.2 2.03
R＝(H
2-CO
2)/(CO+CO
2)
Embodiment 6
Take by weighing Cu-ZnO-ZrO respectively
2/ HZSM-5, Cu-ZnO-Al
2O
3/ HZSM-5, Cu-ZnO-ZrO
2/ HSY and Cu-ZnO-ZrO
2/ Al
2O
3Each 1g of-HZSM-5 dimethyl ether synthetic catalyst is respectively charged in the stainless steel high-pressure reactor, down feeds argon purge 30 minutes at 140 ℃, feeds hydrogen then 240 ℃ of reduction 4 hours, and when logical hydrogen reducing process, controlling heat-up rate is 1 ℃/min.After reduction finishes, feed reactor feed gas and react, unstripped gas consists of: H
239.8%, N
237.2%, CO14.7%, CO
25.92%, CH
42.36%.The unstripped gas of this composition is approaching with the composition that Sweet natural gas air partial oxidation gas making condensation removes behind the water.The experimental result of CO transformation efficiency, dme selectivity and yield of dimethyl ether is listed in table 6 respectively on each catalyzer under differing temps and the pressure, and table 7 is in table 8 and the table 9.As seen, on above catalyzer, use the synthesizing dimethyl ether by synthetic gas that contains a large amount of nitrogen and amounts of carbon dioxide and methane of Sweet natural gas air partial oxidation preparation, can obtain higher carbon monoxide transformation efficiency and higher dme selectivity and yield of dimethyl ether.
Table 6Cu-ZnO-ZrO
2Dimethyl ether synthesis experimental result on the/HZSM-5 catalyzer
Temperature, pressure CO transforms selectivity % DME yield
℃ Mpa leads % DME CO
2CH
4C
2CH
3OH %
240 4.0 67.9 75.7 24.5 - - - 51.4
240 6.0 76.8 76.6 23.4 - - - 58.8
240 8.0 83.5 76.3 23.5 0.25 - - 63.7
250 8.0 90.2 75.9 23.5 0.63 - - 68.5
260 8.0 91.1 77.1 22.5 0.45 - - 70.2
270 8.0 89.6 77.7 21.6 0.40 0.27 - 69.6
280 8.0 86.6 77.9 21.0 0.47 0.39 0.24 67.5
Table 7Cu-ZnO-Al
2O
3Dimethyl ether synthesis experimental result on the/HZSM-5 catalyzer
Temperature, pressure CO transforms selectivity % DME yield
℃ Mpa leads % DME CO
2CH
4C
2CH
3OH %
230 4.0 34.9 67.1 32.6 - 0.32 - 23.4
240 4.0 55.8 69.4 29.6 0.98 0.47 0.13 38.7
240 6.0 71.7 72.4 26.5 0.68 0.39 0.12 51.9
240 8.0 78.2 72.9 26.1 0.65 0.27 0.07 57.0
250 8.0 87.5 73.1 25.4 1.04 0.35 0.10 64.0
260 8.0 90.2 73.9 24.2 1.30 0.52 0.14 66.7
270 8.0 89.8 74.0 23.3 1.56 0.82 0.31 66.5
Table 8Cu-ZnO-ZrO
2Dimethyl ether synthesis experimental result on the/HSY catalyzer
Temperature, pressure CO transforms selectivity % DME yield
℃ Mpa leads % DME CO
2CH
4C
2CH
3OH %
240 4.0 54.9 70.7 28.1 1.18 - - 38.8
240 6.0 66.8 69.1 29.6 1.34 - - 46.2
240 8.0 71.1 70.8 28.0 1.20 - - 50.3
250 8.0 81.1 73.1 27.8 1.15 0.18 0.01 59.3
260 8.0 85.5 73.2 25.3 1.24 0.23 0.01 62.6
270 8.0 87.6 75.1 23.6 0.93 0.30 0.11 65.8
280 8.0 86.8 74.7 23.3 1.24 0.45 0.26 64.8
290 8.0 84.1 75.4 21.4 1.52 0.73 0.55 63.4
Table 9Cu-ZnO-ZrO
2/ Al
2O
3Dimethyl ether synthesis experimental result on the-HZSM-5 catalyzer
Temperature, pressure CO transforms selectivity % DME yield
℃ Mpa leads % DME CO
2CH
4C
2CH
3OH %
240 4.0 50.4 72.3 26.8 0.93 - - 36.4
240 6.0 53.1 74.2 25.3 0.50 - - 39.4
240 8.0 60.1 70.4 28.2 1.42 - - 42.3
250 8.0 76.6 71.6 27.7 0.83 0.15 - 54.8
260 8.0 86.9 73.4 25.5 0.88 0.24 - 63.8
270 8.0 89.6 74.6 24.3 0.85 0.22 0.07 66.8
280 8.0 90.4 75.5 23.0 1.12 0.34 0.13 68.3
290 8.0 88.4 74.9 23.0 1.40 0.48 0.28 66.2
300 8.0 85.1 72.9 23.7 2.05 0.82 0.52 62.0
Claims (4)
1, a kind of method by natural gas via air or oxygen-rich air partial oxidation gas making preparing dimethy ether, it is characterized in that: be that raw material is by the two-stage reaction dimethyl ether synthesis with the Sweet natural gas, first section reaction is that Sweet natural gas and air or oxygen-rich air catalyzing part oxidation are made synthesis gas containing nitrogen, the condition of first section gas making reaction is: 600～960 ℃ of temperature, pressure 0.2～3.0MPa, Sweet natural gas/air when air is raw material=1/1～1/3, when oxygen-rich air is raw material, O in the oxygen-rich air
2/ N
2=1/3.5～1/0.1, Sweet natural gas/oxygen=1/0.2～1/0.7, Sweet natural gas air speed 1000～100000h
-1Second section reaction is after the product with first section reaction removes water, to contain nitrogen, methane and carbonic acid gas the synthetic gas high conversion synthesize dme, the condition of second section dme building-up reactions is: 160 ℃～320 ℃ of temperature, pressure 1.0Mpa～15.0Mpa, unstripped gas air speed 400～10000h
-1
2, by the described method of claim 1, it is characterized in that: in described first section reaction, add CO and H in an amount of water vapour and/or the carbonic acid gas adjusting synthetic gas by natural gas via air or oxygen-rich air partial oxidation gas making preparing dimethy ether
2Ratio, when adding water and/or carbonic acid gas, CH
4/ H
2O=0.1～2.0, CH
4/ CO
2=0.1～2.0.
3, by claim 1 or 2 described methods by natural gas via air or oxygen-rich air partial oxidation gas making preparing dimethy ether, it is characterized in that: adopt supported catalyst at described first section reacting middle catalyst, active ingredient is selected from one or more in nickel, rhodium, the platinum, wherein the loading of metallic nickel is 2～12wt%, the loading of metal rhodium is 0.1～2wt%, and the loading of metal platinum is 0.1～2wt%.
4, by the described method of claim 3 by natural gas via air or oxygen-rich air partial oxidation gas making preparing dimethy ether, it is characterized in that: described catalyzer adopts rare earth or mishmetal and/or alkaline-earth metal to modify, its modification amount is: rare earth metal 0.5～6%, alkaline-earth metal 0.5～5%.
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|---|---|---|---|
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| AU2005335085A1 (en) * | 2005-08-01 | 2007-02-08 | Bp P.L.C. | An integrated process for the co-production of methanol and demethyl ether from syngas containing nitrogen |
| CN101033427B (en) * | 2007-04-04 | 2010-06-23 | 苏宏文 | Dimethyl ether prepared from marsh gas and preparing method for the same |
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