CN101519336A - Method and equipment for producing hydrocarbon with synthetic gas - Google Patents
Method and equipment for producing hydrocarbon with synthetic gas Download PDFInfo
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- CN101519336A CN101519336A CN200810082162A CN200810082162A CN101519336A CN 101519336 A CN101519336 A CN 101519336A CN 200810082162 A CN200810082162 A CN 200810082162A CN 200810082162 A CN200810082162 A CN 200810082162A CN 101519336 A CN101519336 A CN 101519336A
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 57
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 57
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 509
- 239000007789 gas Substances 0.000 claims abstract description 107
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 82
- 230000018044 dehydration Effects 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012495 reaction gas Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 50
- 230000008016 vaporization Effects 0.000 claims description 29
- 238000009834 vaporization Methods 0.000 claims description 28
- 239000002826 coolant Substances 0.000 claims description 15
- 230000033228 biological regulation Effects 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000003507 refrigerant Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000003541 multi-stage reaction Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000000881 depressing effect Effects 0.000 claims 1
- 238000002309 gasification Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 208000005156 Dehydration Diseases 0.000 description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
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- 239000000945 filler Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for producing hydrocarbon with synthetic gas, which comprises essentially the steps as follows: methanol synthetic reaction of the pressurized synthetic gas is implemented in a methanol synthetic reactor, reaction gas is not separated after being output from a reaction tower and enters a methanol dehydrating reactor under the same pressure level so as to implement the methanol dehydrating reaction and generate the hydrocarbon product, the final reaction gas is cooled and separated so as to generate the hydrocarbon product, water and unreacted synthetic gas, and the separated synthetic gas is either discharged for gas-steam integrated gasification combined cycle (IGCC) or taken as recycled synthetic gas and mixed with the raw material synthetic gas in further methanol synthesis, methanol dehydration and product separation besides little discharge.
Description
Technical field
The present invention relates to a kind of with producing hydrocarbon with synthetic gas method and apparatus, belong to field of chemical engineering.
Background technology
The method of the producing hydrocarbon with synthetic gas of producing with coal or Sweet natural gas, a kind of is can make product with the method through the Fischer-Tropsch reaction as South Africa Sasol company, and product mainly is diesel oil and complicated component, the methane content height of generation, generally also need further to change refining and handle, so investment is big with hydrogenation; Another kind is to generate oxycompound methyl alcohol by synthetic gas, generate the dme generation hydro carbons that further dewaters by methanol dehydration again, for example (the 3rd international Coal Chemical Industry of China and coal transform SYMPOSIUM ON HIGH-TECHNOLOGY to the MTG method of Exxon mobil company, in October, 2006, P187), the main products of MTG method is a gasoline, and quality is good, and it is few to generate methane.For existing synthetic gas synthesizing methanol technology, owing to emit a large amount of reaction heat in the synthesizing methanol, and copper base catalyst for methanol is thermo-labile, so must in reaction, remove reaction heat, for example the shell-and-tube methanol column is paid producing steam with the outer feedwater heat absorption of reaction tubes and is moved heat, because it is restricted to move heat energy power, must adopt and remove reaction heat up to the circulation gas of 5～10 times of material synthesis gas, the methanol content that go out in the methyl alcohol building-up reactions gas this moment has only 3～6%, therefore be not suitable for directly going dehydration to generate hydro carbons methyl alcohol in the reaction gas, so the MTG method adopts synthetic gas to synthesize methyl alcohol earlier, then through reaction gas cooling, condensation separation methyl alcohol from synthetic gas again, at last liquid methanol is carried out dehydration reaction as feed vaporization, because the strong reaction heat of methanol dehydration so the MTG method of mobil adopts the recycle ratio up to 9, causes the energy consumption height.
Summary of the invention
The present invention provides the method and apparatus of the single stage method producing hydrocarbon with synthetic gas of a kind of methyl alcohol synthetic ratio height, saving energy for overcoming above-mentioned the deficiencies in the prior art.
Synthesis gas through methanol system hydrocarbon principal reaction process is as follows:
1, synthesizing methanol: CO+2H
2→ CH
3OH+102.5KJ ... (1)
2, methanol dehydration generates hydrocarbon: CH
3OH → H
2O+-CH
2-hydrocarbon+44.73KJ ... (2)
Or methyl alcohol generates dme through dehydration, the dme generation hydrocarbon that dewaters again
CH
3OH→1/2(CH
3)
2O+1/2H
2O+10.08KJ……………………(3)
1/2(CH
3)
2O→-CH
2-+1/2H
2O+34.65KJ…………………………(4)
Therefore above-mentioned reaction all is strong exothermal reactions, if can not in time the reaction liberated heat be removed, then catalyst temperature significantly raises and will make the catalyst overheating inactivation.Increase the heat energy power of moving though adopt shell-and-tube water-cooled fixed-bed reactor can strengthen heat interchanging area, but because of heat-eliminating medium water temperature in the reactor is more or less the same down basically, because catalyzed reaction is carried out on catalyzer and not according to front and back phase uniform velocity, general reactor front portion is from balanced remote, speed of response is fast, it is also many to emit reaction heat, the rear portion is with reacting near balance, speed of response slows down, it is also few to emit reaction heat, and existing as previously mentioned shell-and-tube water-cooled reactor, the same before and after the temperature of refrigerant, if reduce coolant temperature like this, strengthen heat transfer temperature difference and move heat, reach the heat request that moves of top or anterior high speed of response and strong reaction heat, then reactor lower part or rear portion reaction heat reduce, move heat and cause temperature of reaction to descend, speed of response is further slowed down below catalyst activity with regard to stopped reaction, therefore be difficult to the way that makes the best of both worlds of accomplishing that the front and rear part reaction is all carried out under optimal reaction temperature greater than reaction heat.The present invention is directed to this fundamental contradiction, break through existing refrigerant with same temperature, and adopt the different sections of reactor to adopt the differing temps refrigerant to solve, make the size that heat exchange is shifted out by reaction heat in the reaction need design, a plurality of districts before and after specifically can being divided in proper order by reaction gas flow direction in catalyst layer, come indirect heat exchange by refrigerant by heat transfer tube, for picture methyl alcohol building-up reactions, temperature of reaction is in 180 ℃～300 ℃ scopes, can adopt pressurized hot water to make thermophore, the sensible heat that the vaporizing liquid heat absorption absorbs far above the heat-eliminating medium temperature rise in reactor, then need with the low mineral oil of volatility for high reaction temperature more, thermal oil or fused salt are made refrigerant, heat is taken in the drum by cooling circuit, heat is passed to water generates vapor recovery heat by heat transfer tube in the drum.Thermophore is removed the methyl alcohol synthesising reacting heat simultaneously directly during byproduct steam when using water as refrigerant, catalyst for methanol can be contained in the heat transfer tube promptly as the Lurgi shell and tube-type reactor, at this moment heat transfer tube is a reaction tubes, the outer shell side of reaction tubes is a feedwater, catalyzer also can be contained in outside the heat transfer tube, at this moment heat transfer tube is that water pipe is the waterpipe type reactor, and water pipe can be a shell and tube, spiral, and also laterally water pipe is horizontal water-cooled methanol column.The one, different catalysts piece district in front and back adopts the grouping heat transfer tube, every group of heat transfer tube can be communicated with a drum of different pressures for vaporization, vaporization temperature as required, for example reaction is positioned at the vaporization down of the anterior heat transfer tube mesolow low temperature of reaction in earlier stage, increase the heat transfer temperature difference enhancement of heat transfer, solve the reaction problem that anterior speed of response is fast, reaction heat is especially big; Be positioned at reaction rear portion catalyzed reaction speed and reaction heat and reduce, the corresponding raising of heat exchanging water pipe's pressure for vaporization and temperature reduces heat transfer temperature difference, avoids because of rear portion reaction heat reduces, and moves heat too much, and reaction temperature is spent low.The 2nd, drum pressure can be regulated height, along with the catalyzer increase of duration of service, catalyzed reaction advances to the rear portion, when rear portion reaction heat increases, also heat exchanging water pipe's pressure for vaporization in the catalyzer of rear portion can be reduced or link, the later stage water pipe is gasified under low-temp low-pressure strengthen heat transfer temperature difference and heat transfer rate with low-pressure drum.Above-mentioned set of heat exchange tubes and pressure regulation drum pressure for vaporization can be chosen between 0.2～13MPa as required, and in the different catalyzed reaction blocks 81,82,83, set of heat exchange tubes 91,92 coupled pressure regulation drum 71,72 pressure reduction can be at 0.2～7MPa.
The present invention is synthetic by adopting the classification water-cooled reactor to be applied to methyl alcohol, with recycle ratio can by existing 5～10 be reduced to＜2, methanol content brings up to 10～60% by existing 3～6% in the methyl alcohol building-up reactions gas, thereby the synthetic gas of the synthetic high carbinol content that obtains of methyl alcohol is directly advanced the hydrocarbonylation of Dehydration of methanol device without refrigerated separation from gas phase become hydrocarbon products, methanol dehydration is similarly strong exothermal reaction, can adopt the classification water-cooled reactor equally, adopt for example ZSM-5 catalyzer of molecular sieve, 260～420 ℃ of temperature of reaction, optimum 280～380 ℃, and adopt water-cooled boiling water shifting heat, but high pressure steam about the by-product 10Mpa.
The present invention will solve the problem that recycle ratio is big, production concentration is low in the synthetic and methanol dehydration fixed-bed reactor of above-mentioned methyl alcohol, but employing is provided with the methyl alcohol synthetic reactor and the methanol dehydration hydrocarbonylation tower of heat exchanging water pipe's group of many group independent regulation pressures for vaporization and temperature, the strong reaction hot-zone that is implemented in methyl alcohol synthesizing methanol dehydration increases heat transfer temperature difference with vaporization temperature that reduces water in the pipe and pressure and heats and move heat, makes reaction heat keep less heat transfer temperature difference than the sub-district and unlikely temperature is low excessively.
The invention provides a kind of producing hydrocarbon with synthetic gas method, mainly be to add to depress to contain hydrogen, the synthetic gas of components such as carbon monoxide, in methanol sythesis reactor 201, carry out earlier the methyl alcohol building-up reactions, going out the tower reaction gas does not separate, under same pressure rating, enter Dehydration of methanol device 202 again and carry out Dehydration of methanol generation hydrocarbon product, again end reaction air cooling is but separated generation product hydro carbons in the back, water and unreacted synthetic gas, Gas combined cycle generation (IGCC) is removed in isolating synthetic gas discharging, perhaps isolating synthetic gas is except that a small amount of discharging, be re-used as the circulation synthetic gas and mix, carry out methyl alcohol again and synthesize with material synthesis gas, methanol dehydration separates with product.
The invention provides a kind of producing hydrocarbon with synthetic gas method, mainly be but that the pressurization synthetic gas earlier has two piece districts at least by independent regulation refrigerant vaporizes temperature separately at first section, and be preferably in the combination methanol sythesis reactor 201 of water-cooled set of heat exchange tubes of low early and high after temperature catalysis synthesizing methanol under the samming reaction conditions, reach in the reaction gas methanol content greater than 10%, Dehydration of methanol generates hydro carbons in second section Dehydration of methanol device 202 again.
The invention provides a kind of producing hydrocarbon with synthetic gas method, mainly be that the reaction gas that methyl alcohol synthetic reactor advances elder generation's methanol dehydration catalyzed reaction generation dme on the alumina type catalyzer in the Dehydration of methanol device 202, dme and methanol dehydration generate hydro carbons on ZSM-5 equimolecular sieve catalyst again, the reaction gas that perhaps goes out methyl alcohol synthetic reactor directly advances the Dehydration of methanol device, dehydration reaction on ZSM-5 equimolecular sieve catalyst, the Dehydration of methanol temperature is 260～420 ℃, and more excellent is 280～380 ℃.
The invention provides a kind of producing hydrocarbon with synthetic gas method, the ratio that mainly is circulation synthetic gas and material synthesis gas in the synthetic gas of into methyl alcohol synthetic reactor is preferably less than 2 less than 4.
The invention provides a kind of producing hydrocarbon with synthetic gas equipment, mainly form by methanol sythesis reactor and Dehydration of methanol device polyphone, first section methanol sythesis reactor has the water-cooled combination methanol sythesis reactor 201 of two set of heat exchange tubes blocks at least, but each set of heat exchange tubes 91,92 and drum 71,72 bindings of independent regulation pressure for vaporization separately, constitute the circulation loop of different pressures for vaporization and coolant temperature, with the vaporization temperature of regulating various heat exchange pipe group 91,92, reduce the methanol synthesis catalyst bed temperature difference.Second section Dehydration of methanol device after being connected in is taken to the Dehydration of methanol device 202 in rare two piece districts, but the drum 71,72 of each set of heat exchange tubes 91,92 and independent regulation pressure for vaporization links, constitute the circulation loop of different pressures for vaporization and coolant temperature, with regulating the drum pressure for vaporization that each heat exchange water cooling tube group links to each other, remove catalyst layer reaction heat by the heat absorption of the water in water pipe vaporization, dwindle the dehydration reaction beds temperature difference.
The invention provides a kind of producing hydrocarbon with synthetic gas equipment, but mainly be to have at least the catalyzed reaction block 81,82,83 of three set of heat exchange tubes 91,92,93 of independent regulation coolant temperature to form the composite reaction district in the Dehydration of methanol device housing 1, form by having γ-aluminum oxide or molecular sieve methanol dehydration catalyst and lower reaction zone piece 82,83 to have ZSM-5 molecular sieve analog methyl alcohol and dme dehydration to generate the hydro carbons catalyst layer in the top reaction block 81 in the same reactor shell 1.
In a better example of the present invention, but described method is the Dehydration of methanol device is to have two piece districts at least by the composite reaction equipment of the set of heat exchange tubes of independent regulation coolant temperature separately, the refrigerant in wherein one or more heat transfer block districts with high temperature heat conductive oil or fused salt take out of heat outside reactor drum or vapour generator in heating boiler water generates high pressure steam.
In a better example of the present invention, described method is the many groups set of heat exchange tubes in methanol sythesis reactor and the Dehydration of methanol device, when reduction of driving catalyzer temperature-elevating or catalyst regeneration, available high-temperature steam or heat-conducting oil heating catalyzer elevated temperature carry out the reduction or the regeneration of catalyzer.
In a better example of the present invention, described method can be applicable to by synthetic gas system gasoline, diesel oil, propylene, ethene, aliphatic hydrocarbon or aromatic hydrocarbons, isoparaffin, normal paraffin and naphthenic hydrocarbon.
Description of drawings
Fig. 1 is the schematic flow sheet of synthetic gas by the methanol by one-step method synthin.
Fig. 2 is that synthetic gas is by the schematic flow sheet of methanol by one-step method synthin in conjunction with IGCC.
Fig. 3 is methyl alcohol synthetic reactor or methanol dehydration tower synoptic diagram.
Fig. 4 is the reactor synoptic diagram of three groups of methanol dehydration catalysts at same housing.
Embodiment
Below in conjunction with accompanying drawing technical scheme of the present invention is described in detail.
Fig. 1 is the schematic flow sheet of synthetic gas by the methanol by one-step method synthin.Can to be raw material with coal make synthetic gas or make with conversion of natural gas through water-gasization or fine coal pure oxygen or oxygen-rich gasification etc. unstripped gas 101, contains H
2, CO and a small amount of CO
2, CH
4, N
2Deng, hydrogen-carbon ratio 0.7～2.5, pressure 2～15MPa.Unstripped gas 101 merges into gas 103 with circulation gas 102 by circulator 207, being heated to synthetic gas 103 about 210 ℃ through gas-gas interchanger 203 enters methanol sythesis reactor 201 and carries out the methyl alcohol building-up reactions, but methanol sythesis reactor 201 has the set of heat exchange tubes such as the accompanying drawing 3 of 2 groups of independent regulation pressures for vaporization and temperature at least, go out methanol sythesis reactor 201 and contain the methyl alcohol volume fraction greater than 10% synthetic gas 104 and exhaust gas 105 heat exchange through gas-gas interchanger 204 and Dehydration of methanol device 202, enter Dehydration of methanol device 202 for about 300 ℃ to temperature, on methanol dehydration catalyst, carry out Dehydration of methanol, the outlet reaction gas is through gas-gas interchanger 204,203 heat exchange cool to about 100 ℃, being cooled to about 40 ℃ of hydrocarbon 108 and water 107 through vapour liquid separator 206 separating and condensings through water cooler 205 is discharged by liquid phase, gas 106 goes through blow-off valve 210 effluxes other usefulness except that a small amount of off-gas 109, converges through circulator 207 and fresh feed gas 101 as circulation gas 102 and removes synthesizing methanol again.209 and the 208 shortcut valves that are respectively conditioned reaction device 201 and 202 inlet air temperature among the figure.
Fig. 2 is that synthetic gas is by the schematic flow sheet of methanol by one-step method synthin in conjunction with IGCC, Fig. 2 is different with Fig. 1 to be that synthetic gas does not circulate, disposable by methyl alcohol synthetic and Dehydration of methanol device, the gas 106 that comes out from vapour liquid separator 206 all removes IGCC as off-gas 109, it is the gas-steam combined circulating generation, unstripped gas 101 is into synthetic tower gas, is heated to through gas-gas interchanger 203 to enter methanol sythesis reactor 201 about 210 ℃ and carry out the methyl alcohol building-up reactions.Fig. 2 rest part is identical with Fig. 1.
Fig. 3 is horizontal water pipe methanol sythesis reactor or the Dehydration of methanol device synoptic diagram that two drums are arranged, and describes with methanol sythesis reactor 201 at this.Form by methanol sythesis reactor 201 and drum 71,72 bindings, steam outlet pipe 41,42 and filler pipe 21,22 that the carrying vapour regulated valve is arranged respectively on the drum 71,72, methanol sythesis reactor 201 is by housing 1, reaction gas inlet 2 on the housing 1 and reaction gas outlet 3, the porous gas collection plate 5 of the porous gas sparger 4 at housing 1 top and bottom, 6,7 on both sides dividing plate is equipped with two groups of catalyst layers 81,82 in the housing 1, and heat-eliminating medium moves set of heat exchange tubes 91,92 compositions of heat in the catalyst layer 81,82.The pump circulation loop that respectively has water pump 31,32 and carbonated drink pipe 61,62 to constitute between two drums and set of heat exchange tubes on water inlet pipe 51,52 circuits of the set of heat exchange tubes 91,92 of drum 71,72 and methanol sythesis reactor 201, adopt water pump to improve the circulating cooling medium flow, can improve heat-transfer effect; Set of heat exchange tubes is the straight tube that all there is header at two ends, 4 tube banks are arranged among the figure, respectively there is a header at each tube bank two ends, the left and right sides, left end header 601,602,603,604 links with the import and export pipe respectively, link with communicating pipe 801,802 respectively between the adjacent header 701 of right-hand member and 702,703 and 704, set of heat exchange tubes 91 constitutes first circulation loop with drum 71, pump 31 and turnover pipeline 51,61, and set of heat exchange tubes 92 constitutes second circulation loop with drum 72, pump 32 and turnover pipeline 52,62.Above-mentioned set of heat exchange tubes 91,92 all can increase by 2,4,6 as required ... individual tube bank links with communicating pipe between neighbouring header.Fig. 3 be used for methyl alcohol when synthetic in dress copper base catalyst for methanol, then adorn catalyzer such as molecular sieve when being used for methanol dehydration.
Fig. 4 is the reactor synoptic diagram of three groups of methanol dehydration catalysts at same housing.Lower leaf is contained in the synoptic diagram of a reactor on the methanol dehydration catalyst, is the horizontal composite reaction equipment of many groups U-shaped pipe that three drums are arranged among the figure.Form by Dehydration of methanol device 202 and drum 71,72,73 bindings, steam outlet pipe 41,42,43 and filler pipe 21,22,23 that the carrying vapour regulated valve is arranged respectively on the drum 71,72,73, Dehydration of methanol device 202 is by housing 1, reaction gas inlet 2 on the housing 1 and reaction gas outlet 3, the porous gas collection plate 5 of the porous gas sparger 4 at housing 1 top and bottom, 6,7 on both sides dividing plate is equipped with three groups of catalyst layers 81,82,83 in the housing 1, and heat-eliminating medium moves U-shaped set of heat exchange tubes 91,92,93 compositions of heat in the catalyst layer 81,82,83.Set of heat exchange tubes 91 among the figure, 92,93 are made up of the U-shaped pipe, U-shaped tube opening two ends and header 601,602 ... 606 are communicated with, header 602,604,606 respectively through coolant inlet pipe 51,52,53 link drum 71,72,73, header 601,603,605 respectively through coolant outlet pipe 61,62,63 link drum 71,72,73, constitute three groups of set of heat exchange tubes 91,92,93 and drum 71,72,73 coolant circulation circuit, as coolant temperature lower (＜300 ℃) directly water set of heat exchange tubes circulation as figure in drum 71 banded set of heat exchange tubes 91, preferably as need high coolant temperature (300～350 ℃) with 350 ℃ of thermal oil or fused salts (〉) take heat out of, as drum among the figure 72,73 banded set of heat exchange tubes 92,93 take heat out of for thermal oil passes through drum 72, heat transfer tube in 73 is passed to water generates steam, catalyst layer 81 dress γ-aluminum oxide methanol dehydrations become dimethyl ether catalyst, catalyst layer 82,83 dress ZSM-5 equimolecular sieve methanol dehydration catalysts, set of heat exchange tubes 91,92,93 also can have the straight tube of header as Fig. 3 two ends, and set of heat exchange tubes 93 bottoms and 5 of porous gas collection plates can be established the adiabatic catalyst layer when needing.
Embodiment 1: with synthetic gas system gasoline production flow process such as Fig. 1, methanol sythesis reactor 201 adopts as the horizontal classification water-cooling tower of Fig. 3,4.0 meters of diameters, interior dress copper base catalyst for methanol 150M
3, Dehydration of methanol device 202 adopts as the horizontal water-cooling tower of Fig. 4,3.8 meters internal upper part catalyst layers of diameter, 81 dress γ-aluminum oxide 30M
3, middle and lower part catalyst layer 82,83 dress ZSM-5 molecular sieve catalyst 100M
3, compressed synthetic gas and circulation gas to 6MPa converges, and advances methanol sythesis reactor 201 up and down through being heated to 230 ℃, under 250 ℃ of left and right sides temperature, carries out the methyl alcohol building-up reactions on the catalyst for methanol layer.Reaction heat is synthesized the water absorption in the horizontal water pipe in the tower and byproduct steam, and the vapor pressures in drum 71 pressure ratios 72 hang down about 1Mpa, go out CH in the methyl alcohol synthetic reactor gas
3OH content 40.2% enters 202 dehydrations of Dehydration of methanol device with 300 ℃ of hydrocarbonylation tower exhaust gas heat exchange and generates hydrocarbon.The Dehydration of methanol device adopts Fig. 4 structure, catalytic reaction zone 81 in top water-cooled set of heat exchange tubes 91 generates dme earlier, in the catalyzed reaction block 82,83 of middle and lower part thermal oil set of heat exchange tubes 92,93, dehydration generates hydrocarbon, by-product 10Mpa high pressure steam under temperature about in the of 350 ℃ again.Make hydrocarbon 110 ton per days by material gas quantity 10268kmol/h, produce 35.6 ten thousand tons of hydrocarbon per year, 1000Nm
3Synthetic gas gets hydrocarbon up to 194kg, and data see attached list 1.
Embodiment 2: see Fig. 2 with one-step method from syngas system gasoline in conjunction with the IGCC Production Flow Chart, methanol sythesis reactor 201 adopts as the horizontal classification water-cooling tower of Fig. 3,3.5 meters of diameters, interior dress copper base catalyst for methanol 110M
3, Dehydration of methanol device 202 adopts as the horizontal water-cooling tower of Fig. 3, adorns ZSM-5 molecular sieve catalyst 90M in 3.3 meters of the diameters
3, compressed synthetic gas to 5.5MPa advances methanol sythesis reactor 201 through being heated to 220 ℃, under 250 ℃ of left and right sides temperature, carries out the methyl alcohol building-up reactions on the catalyst for methanol layer.Reaction heat is synthesized in the tower that water in the horizontal water pipe absorbs and byproduct steam goes out CH in methanol sythesis reactor 201 gases
3OH content 46% ℃ enters 202 dehydrations of Dehydration of methanol device with the 202 exhaust gas heat exchange to 300 of Dehydration of methanol device and generates hydrocarbon.Recycle ratio is zero in this example, and the 2772kmol/h that speeds to exit all goes the IGCC generating, makes hydrocarbon 798.4 ton per days by material gas quantity 10000kmol/h, produces 26.5 ten thousand tons of hydrocarbon per year, 1000Nm
3Synthetic gas gets hydrocarbon 149kg, and data see attached list 2.
Beneficial effect
Compared with the prior art the present invention has significant advantage, the one, to the different pressures for vaporization and the gasification temperature of reactor different piece catalyst layer set of heat exchange tubes employing heat transferring medium, fast to speed of response especially, the previous section that reaction heat is big, adopt the low-pressure low-temperature vaporization to strengthen heat transfer temperature difference and fully remove reaction heat, make not overtemperature of catalyzer, speed of response and reaction heat smaller portions then adopt higher pressure for vaporization and temperature, avoid moving heat too much, make temperature low excessively, thereby make recycle ratio than prior art fall be several times lower than many, as recycle ratio among the embodiment 1 is 0.4, recycle ratio was zero when synthetic gas system hydrocarbon was in conjunction with IGCC among the embodiment 2, be that synthetic gas once passes through, methyl alcohol is synthesized with dehydration loop tolerance significantly to be reduced, thereby reduced the equipment size of synthesizer significantly, both significantly saved investment, created favourable condition for maximizing again.The 2nd, reduce recycle ratio while methanol content and reach 10～60%, improve several times than prior art, thereby reaching the circulator power consumption reduces at double with the reduction of recycle ratio, the pure and mild ton of ton hydrocarbon reclaims reaction heat and the byproduct steam amount significantly improves, significantly reduce and be used to cool off the water cooler consumption of cooling-water that reaction gas uses, therefore cut down the consumption of energy significantly, reach energy-saving and cost-reducing unusual effect.The 3rd, different catalysts and catalyzer different sites temperature of reaction can be regulated according to the independence and freedom that requires of reaction, for example 300 ℃ of lesser tempss up and down can be kept with γ-aluminium oxide catalyst in methanol dehydration tower top, 350 ℃ of comparatively high tempss up and down can be kept with ZSM-5 molecular sieve in the middle and lower part, and for example react the situation of moving behind the focus according to different times catalyst activity decline before and after the reaction, adjust top and the bottom catalyst layer heat transfer tube pressure for vaporization, gasification temperature, make catalyzer performance best effect.The 4th, go out methanol content high in the methanol column reaction gas, producing hydro carbons for synthetic gas adopts the fixed-bed reactor one-step method from syngas to create condition, than the reaction gas of the high several times methanol content of prior art, the hydrocarbon content that generates through the methanol dehydration catalyst dehydration improves several times.
More than by numerous legends and embodiment abundant description done in theme of the present invention, according to design of the present invention spirit, those of ordinary skill in the art can easily carry out in various variations and the synthesis gas through methanol system of the being applied to hydrocarbon.In the combined reactor of the present invention during the set of heat exchange tubes water, the water pipe that drum comes can be communicated with the water inlet of water pump pump circulation, also can be without water pump, intake with natural circulation, the also available multi-group valved tube of each drum is communicated with each group heat transfer tube, water inlet pipe and water outlet pipe can be by valve regulated, and the one group of heat transfer tube that also can not have valve is to a drum.Heat transfer tube can be that pipe also can be flat tube or heat exchanger plates, and heat transferring medium is water or thermal oil and fused salt.
When reaction gas enters catalyzer and begins to react, general temperature is lower, so before set of heat exchange tubes, also the adiabatic section can be set, but this adiabatic section catalytic amount should be no more than 1/10th of total amount after reduction is shunk, for example dehydration reactor also can be provided with the adiabatic section behind the heat exchange conversion zone at the catalyzer rear portion, can satisfy the needs of reaction later stage raising temperature.
Claims (10)
1. the method for a producing hydrocarbon with synthetic gas, it is characterized in that adding depressing and contain hydrogen, the synthetic gas of components such as carbon monoxide, earlier in methanol sythesis reactor (201), carry out the methyl alcohol building-up reactions, going out the tower reaction gas does not separate, under same pressure rating, enter Dehydration of methanol device (202) again and carry out Dehydration of methanol generation hydrocarbon product, again end reaction air cooling is but separated generation product hydro carbons in the back, water and unreacted synthetic gas, Gas combined cycle generation (IGCC) is removed in isolating synthetic gas discharging, perhaps isolating synthetic gas is except that a small amount of discharging, be re-used as the circulation synthetic gas and mix, carry out methyl alcohol again and synthesize with material synthesis gas, methanol dehydration separates with product.
2. according to the method for the described producing hydrocarbon with synthetic gas of claim 1, but the synthetic gas that it is characterized in that pressurizeing earlier has two piece districts at least by independent regulation refrigerant vaporizes temperature separately at first section, and be preferably in the methanol sythesis reactor (201) of water-cooled set of heat exchange tubes of low early and high after temperature catalysis synthesizing methanol under the samming reaction conditions, adopt copper base catalyst for methanol to be issued in the reaction gas methanol content greater than 10%, again Dehydration of methanol generation hydro carbons in second section Dehydration of methanol device (202) at 200～300 ℃.
3. according to the method for the described producing hydrocarbon with synthetic gas of claim 1, the reaction gas that it is characterized in that methyl alcohol synthetic reactor advances elder generation's methanol dehydration catalyzed reaction generation dme on the alumina type catalyzer in the Dehydration of methanol device (202), dme and methanol dehydration generate hydro carbons on ZSM-5 equimolecular sieve catalyst again, the reaction gas that perhaps goes out methyl alcohol synthetic reactor directly advances the Dehydration of methanol device, dehydration reaction on ZSM-5 equimolecular sieve catalyst, the Dehydration of methanol temperature is 260～420 ℃, and more excellent is 280～380 ℃.
4. according to the method for the described producing hydrocarbon with synthetic gas of claim 1, the ratio that it is characterized in that circulation synthetic gas and material synthesis gas in the synthetic gas of methyl alcohol synthetic reactor into is preferably less than 2 less than 4.
5. according to the equipment of the described producing hydrocarbon with synthetic gas method of claim 1, it is characterized in that forming by methanol sythesis reactor and Dehydration of methanol device polyphone, first section methanol sythesis reactor has the water-cooled combination methanol sythesis reactor (201) of two set of heat exchange tubes blocks at least, each set of heat exchange tubes (91), (92) but with the drum of independent regulation pressure for vaporization (71), (72) link separately, constitute the circulation loop of different pressures for vaporization and coolant temperature, with the vaporization temperature of regulating various heat exchange pipe group (91), (92), reduce the methanol synthesis catalyst bed temperature difference.
6. according to the equipment of the described producing hydrocarbon with synthetic gas method of claim 1, it is characterized in that forming by methanol sythesis reactor and Dehydration of methanol device polyphone, second section Dehydration of methanol device after being connected in is taken to the Dehydration of methanol device (202) of rare two set of heat exchange tubes blocks, each set of heat exchange tubes (91,92) but with the drum (71 of independent regulation pressure for vaporization, 72) link, constitute the circulation loop of different pressures for vaporization and coolant temperature, with regulating the drum pressure for vaporization that each set of heat exchange tubes links to each other, remove catalyst layer reaction heat by the heat absorption of the water in water pipe vaporization, dwindle the dehydration reaction beds temperature difference.
7. according to the equipment of the described producing hydrocarbon with synthetic gas method of claim 1, it is characterized in that Dehydration of methanol device housing (1) but in have at least three set of heat exchange tubes (91), (92), the catalyzed reaction block (81) of (93), (82), (83) of independent regulation coolant temperature to form the composite reaction district, form by having γ-aluminum oxide or molecular sieve methanol dehydration catalyst and lower reaction zone piece (82), (83) to have ZSM-5 molecular sieve analog methyl alcohol and dme dehydration to generate the hydro carbons catalyst layer in the reaction block of the top in the same reactor shell (1) (81).
8. according to the method for the described producing hydrocarbon with synthetic gas of claim 1, it is characterized in that but the Dehydration of methanol device is to have two piece districts at least by the composite reaction equipment of the set of heat exchange tubes of independent regulation coolant temperature separately, the refrigerant in wherein one or more heat transfer block districts with high temperature heat conductive oil or fused salt take out of heat outside reactor drum or vapour generator in heating boiler water generates high pressure steam.
9. according to the method for the described producing hydrocarbon with synthetic gas of claim 1, it is characterized in that the many groups set of heat exchange tubes in methanol sythesis reactor and the Dehydration of methanol device, when reduction of driving catalyzer temperature-elevating or catalyst regeneration, available high-temperature steam or heat-conducting oil heating catalyzer elevated temperature carry out the reduction or the regeneration of catalyzer.
10. according to the method for the described producing hydrocarbon with synthetic gas of claim 1, it is characterized in that can be applicable to by synthetic gas system gasoline, diesel oil, propylene, ethene, aliphatic hydrocarbon or aromatic hydrocarbons, isoparaffin, normal paraffin and naphthenic hydrocarbon.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100821629A CN101519336B (en) | 2008-02-29 | 2008-02-29 | Method and equipment for producing hydrocarbon with synthetic gas |
| PCT/CN2008/072750 WO2009052764A1 (en) | 2007-10-19 | 2008-10-20 | A composite reaction apparatus and the chemical production method using the same |
| EP08841333.1A EP2213367A4 (en) | 2007-10-19 | 2008-10-20 | A composite reaction apparatus and the chemical production method using the same |
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| CN2008100821629A CN101519336B (en) | 2008-02-29 | 2008-02-29 | Method and equipment for producing hydrocarbon with synthetic gas |
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Cited By (8)
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| CN103270139A (en) * | 2010-11-09 | 2013-08-28 | 普里默斯绿色能源公司 | Single loop multistage fuel production |
| CN103694074A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | System and process for preparing olefin by taking coal and coke-oven gas as raw materials |
| CN104117380A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Process for production of hydrocarbons by synthetic gas conversion and catalysts used for process |
| CN104399413A (en) * | 2014-11-18 | 2015-03-11 | 安徽新月化工设备有限公司 | Controllable heat-removing reactor |
| CN104419440A (en) * | 2013-08-22 | 2015-03-18 | 杭州林达化工技术工程有限公司 | Method and apparatus for producing hydrocarbons by synthesis gas from coal |
| CN106085491A (en) * | 2016-06-28 | 2016-11-09 | 山西沸石科技有限公司 | A kind of by synthesis gas enriched Gas body, liquefied petroleum gas and the method for gasoline |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181023C (en) * | 1999-09-07 | 2004-12-22 | 犹德有限公司 | Method and arrangement for producing methanol |
| GB0301323D0 (en) * | 2003-01-21 | 2003-02-19 | Johnson Matthey Plc | Methanol synthesis |
| DE10345902B4 (en) * | 2003-10-02 | 2005-07-07 | Lurgi Ag | Production of synthesis gas from natural gas involves effecting both the reforming of a natural gas/steam mixture and also cooling of the obtained synthesis gas in a closed vertical reactor |
| CN1857766B (en) * | 2005-04-30 | 2010-12-01 | 杭州林达化工技术工程有限公司 | Heat exchanging reactor |
| CN100523132C (en) * | 2007-06-13 | 2009-08-05 | 中国石油天然气集团公司 | Method for carrying Fischer-Tropsch synthesis by using fixed bed device |
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2008
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| CN103270139A (en) * | 2010-11-09 | 2013-08-28 | 普里默斯绿色能源公司 | Single loop multistage fuel production |
| CN103270139B (en) * | 2010-11-09 | 2015-11-25 | 普里默斯绿色能源公司 | Single loop multistage fuel production |
| CN104117380A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Process for production of hydrocarbons by synthetic gas conversion and catalysts used for process |
| CN104117380B (en) * | 2013-04-26 | 2019-05-14 | 中国科学院大连化学物理研究所 | The technique and used catalyst of synthesis gas conversion production hydrocarbon compound |
| CN104419440A (en) * | 2013-08-22 | 2015-03-18 | 杭州林达化工技术工程有限公司 | Method and apparatus for producing hydrocarbons by synthesis gas from coal |
| CN103694074A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | System and process for preparing olefin by taking coal and coke-oven gas as raw materials |
| CN104399413A (en) * | 2014-11-18 | 2015-03-11 | 安徽新月化工设备有限公司 | Controllable heat-removing reactor |
| CN106085491A (en) * | 2016-06-28 | 2016-11-09 | 山西沸石科技有限公司 | A kind of by synthesis gas enriched Gas body, liquefied petroleum gas and the method for gasoline |
| CN106085491B (en) * | 2016-06-28 | 2018-01-16 | 山西沸石科技有限公司 | A kind of method by synthesis gas enriched Gas body, liquefied petroleum gas and gasoline |
| CN106179149A (en) * | 2016-08-22 | 2016-12-07 | 中国神华能源股份有限公司 | The reaction unit of methanol-to-olefins |
| CN111974315A (en) * | 2020-09-04 | 2020-11-24 | 张家港市江南锅炉压力容器有限公司 | Fluidized reaction system |
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