CN101745351B - Fischer-Tropsch process device and technology - Google Patents
Fischer-Tropsch process device and technology Download PDFInfo
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- CN101745351B CN101745351B CN 200910215318 CN200910215318A CN101745351B CN 101745351 B CN101745351 B CN 101745351B CN 200910215318 CN200910215318 CN 200910215318 CN 200910215318 A CN200910215318 A CN 200910215318A CN 101745351 B CN101745351 B CN 101745351B
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Abstract
The invention relates to a Fischer-Tropsch process device and a technology, belonging to the technical field of Fischer-Tropsch process realization. Based on loop free series-wound multi-level fixed bed reactors, the invention mainly aims at synthesis gas prepared by air or oxygenized air rather than non-pure oxygen gasification. The synthesis gas is rich in nitrogen, inert gas and other non-effective gases, and the conversion ratio of the reaction system at each level is controlled well, thereby effectively solving the heat transmission problem inside the reactors. The reaction system at each level is provided with independent hydrogen supply to use a small amount of hydrogen to adjust C/H ratio of gas pre-entering the reaction system at the level, thereby realizing preset conversion ratio of the synthesis gas, greatly reducing deactivation rate of catalyst, improving operation stability of the reactor and reducing operation cost. The method has obvious effect for a second-level reactor and subsequent reactors.
Description
[technical field]
The present invention relates under catalyst action, the synthesis gas that will contain hydrogen and carbon monoxide is converted into the Fischer-Tropsch synthesis of liquid hydrocarbon compound, is specifically related to Fischer-Tropsch synthesizer and technique.
[background technology]
Fischer-Tropsch synthesis is the chemical process that the hydrogen in the synthesis gas and carbon monoxide is converted into hydrocarbon mixture, synthesis gas can come from the gasification product of the hydrocarbons such as coal, natural gas, living beings, coke-stove gas or the refinery dregs of fat, and synthetic catalyst can be that iron-based also can be cobalt-base catalyst.In general, ferrum-based catalyst adopts the precipitation method to produce, and the carrier that cobalt-base catalyst adopts is aluminium oxide, silica, titanium oxide, active carbon, or their combination.The synthetic target product of Fischer-Tropsch can be the hydrocarbon products such as gasoline, diesel oil, lubricating oil, aviation kerosine or wax.According to different business goal products, Fischer-Tropsch is synthetic can to adopt dissimilar reactors, and for the project take diesel oil and wax as target product, present trend is to adopt slurry attitude bed or fixed bed reactors.
Although adopt the fischer-tropsch reaction process of fixed bed reactors before half a century, just to realize industrialization still having problems perplexing people, have a strong impact on the stable operation of device always.In these problems, removing with the inactivation problem of catalyst of reaction heat is particularly outstanding.Because Fischer-Tropsch synthesis is strong exothermal reaction, if reaction heat does not have and can in time remove, hot localised points just appears in catalyst easily, cause the inactivation of catalyst and the elective reduction of long chain alkane product, the moment temperature runaway phenomenon that can occur reactor in the serious situation, the device parking maintenance of having to.Adopting paste state bed reactor is to solve Fischer-Tropsch synthesis to move one of effective means of heat problem, especially all the more so concerning large-scale device, but the use of paste state bed reactor also brings new problem.In paste state bed reactor, tiny catalyst granules and liquid hydrocarbon product mix, their effective separation difficulty is in fact and not second to other technical barriers that faces, the solution filter price that can realize to a certain extent at present ON-LINE SEPARATION is very expensive, this is the problem conscientiously assessing from investing of having to concerning middle-size and small-size Fischer-Tropsch complex item.In addition, people know little to the three-phase fluid mechanical behavior in the slurry attitude bed, and this brings certain difficulty also for the amplification of paste state bed reactor.On the contrary, people have in theory had very deep understanding to fixed bed reactors, and there are not the separation problem of catalyst and fluid product in fixed bed reactors, therefore, the small-scale Fischer-Tropsch complex item of centering, fixed bed reactors remain a kind of selection that suitable attraction is arranged.
Another synthetic outstanding problem of Fischer-Tropsch is the easy inactivation of catalyst.Water is one of synthetic product of Fischer-Tropsch, no matter but concerning ferrum-based catalyst or cobalt-base catalyst, water all can cause the inactivation of catalyst, therefore, the conversion per pass of carbon monoxide all can't be too high in the reactor, and not so the rapid deactivation of catalyst will be so that install and can't normally move.Report that in the fixed bed reactors that adopt ferrum-based catalyst, because the inactivation of catalyst causes reactor can't satisfy set production capacity designing requirement, more catalyst changeout generally namely need stop about three months.
In traditional technique, the preparation great majority of synthesis gas all adopt pure oxygen gasification, approximately contain 1/3rd carbon monoxide in the synthesis gas, 2/3rds hydrogen.For the synthetic total conversion of the Fischer-Tropsch that improves synthesis gas, mostly adopt the reactor tail gas recirculating process, like this can be in the not too high situation of conversion per pass, so that total conversion can satisfy the designing requirement of device, simultaneously owing to contain a considerable amount of inert substances in the recycled offgas, this can help to solve the heat problem that moves of reactor to a certain extent, and the inactivation that slows down catalyst.But for the synthesis gas that adopts the air gasification preparation, because effectively the concentration of synthesis gas (co hydrogenation gas) is very low in reactor outlet tail gas, exhaust gas recirculation will cause the volume of fischer-tropsch reactor too huge, and the aerodynamic efficiency of catalyst reduces.On the other hand, in order to guarantee the high synthesis gas total conversion of reaction system, the circulation of tail gas amount requires very large usually, and this stability to recycle compressor has also proposed extra requirement.Under any circumstance, for a certain reason so that the internal circulating load of tail gas does not reach designing requirement, reactor will move under too small air speed, cause the rapid deactivation of catalyst.
Having necessarily has the fischer-tropsch synthesis process of industrial value process to be, whole reactor assembly can keep the high conversion of synthesis gas with the design production capacity of implement device, the deactivation rate of catalyst must be enough low, system can need not to stop and carry out catalyst regeneration or replacing the sufficiently long time of stable operation like this, simultaneously, reaction heat can be removed timely and effectively.
[summary of the invention]
The invention reside in the inactivation problem with catalyst of removing that solves reaction heat in the fischer-tropsch reaction process, synthetic for the Fischer-Tropsch of the synthesis gas of air gasification preparation especially, a kind of Fischer-Tropsch synthesizer and corresponding technique are provided.
Above-mentioned purpose is realized by following technical scheme:
A kind of Fischer-Tropsch synthesizer is used for by the Fischer-Tropsch of the standby synthesis gas of normal air or oxygen-enriched air vaporizing system synthetic; It is characterized in that, comprise the reaction system of the loop-free at least two-stage series connection of tail gas, every first order reaction system comprises fixed bed reactors and the high-temperature separator that is linked in sequence and cold catch pot; The entrance of first order reaction system is provided with synthesis gas feed pipeline, and the cold catch pot of upper level connects the fixed bed reactors of next stage, and the fixed bed reactors of every first order reaction system are equipped with independent side line hydrogen feed pipeline.
A kind of fischer-tropsch synthesis process based on said apparatus is characterized in that, comprising:
(1) supply with by normal air or the standby synthesis gas of oxygen-enriched air vaporizing system, wherein to add the shared volume ratio of carbon monoxide be the synthesis gas of 50%-80% to hydrogen;
(2) synthesis gas successively by the reaction system of described at least two-stage series connection, carries out respectively Fischer-Tropsch synthetic and separating hydrocarbons product and water without circularly;
In the process (2), according to the hydrogen-carbon ratio that enters in advance in this order reaction system gas, control the hydrogen supply of corresponding side line hydrogen feed pipeline, and the conversion ratio of controlling every first order reaction system is 30%-70%.
Fischer-Tropsch synthesizer and technique that the present invention proposes are based on the multistage fixed bed reactor without circulating series, mainly for adopting air or oxygen-enriched air but not the synthesis gas of pure oxygen gasification preparation.There are the non-effective gases such as a large amount of nitrogen and inert gas in the synthesis gas, and control the conversion ratio of every first order reaction system well, can effectively help to solve the heat problem that moves of inside reactor.Every first order reaction system all is provided with independently hydrogen supply, utilize a small amount of hydrogen to regulate the C/Hratio that enters in advance in this order reaction system gas, can be when realizing set synthesis gas conversion ratio, reduce to a great extent the deactivation rate of catalyst, improve the operation stability of reactor and reduce running cost.This method is especially remarkable on the impact of the second level and reactor subsequently.
[description of drawings]
Fig. 1 is based on the composition schematic diagram of the Fischer-Tropsch synthesizer of multistage fixed bed reactor.
Label declaration among Fig. 1:
1-first order fixed bed reactors 2-first order high-temperature separator 3-first order cold catch pot
The high-temperature separator 6-second level, the fixed bed reactors 5-second level, 4-second level cold catch pot
7-synthesis gas 8-side line hydrogen make-up 9-side line hydrogen make-up
10-first order reactor feedstocks gas 11-first order reactor discharging 12-paraffin is major product
Tail gas 14-petrol and diesel oil is major product 15-water in the middle of the 13-first order
16-first order tail gas 17-side line hydrogen make-up 18-second level reactor feedstocks gas
19-second level reactor discharging 20-paraffin is tail gas in the middle of the major product 21-second level
The product water 24-second level, the product petrol and diesel oil 23-second level, 22-second level tail gas
[specific embodiment]
As shown in Figure 1, this Fischer-Tropsch synthesizer is the two-stage series connection reactor assembly, but need not be confined to two-stage series connection in concrete the application, extends to three grades or more multistage reactor train according to same pattern, and without prejudice to spirit of the present invention.Particularly, the first order reaction system high-temperature separator 2 and the cold catch pot 3 that comprise fixed bed reactors 1 and be linked in sequence; High-temperature separator 5 and cold catch pot 6 that second level reaction system comprises fixed bed reactors 4 and is linked in sequence; The entrance of first order fixed bed reactors 1 is provided with synthesis gas feed pipeline, the cold catch pot 6 of first order reaction system connects the fixed bed reactors 4 of second level reaction system, and the fixed bed reactors of first, second order reaction system all are provided with independent side line hydrogen feed pipeline.
Wherein, exchange heat around the internal heat transfer system of Fischer-Tropsch synthesis device, reactor and utilize method and temperature control and the compress control method of each unit and stream strand are known by the public already, on university textbook, can both obtain these data, thereby at Fig. 1 and providing no longer in detail herein.
The synthesis gas that the present invention adopts refers to: by the standby synthesis gas of air (normal air or oxygen-enriched air) vaporizing system, the content that its effective synthesis gas hydrogen adds carbon monoxide accounts for 50%-80% (if by pure oxygen preparation, its effective synthesis gas content is generally more than 90%), hydrogen-carbon ratio (H
2/ CO volume ratio) between 1.6-2.3, is preferably between the 1.8-2.1; In addition, synthesis gas is before entering the Fischer-Tropsch synthesizer, and wherein water and carbon dioxide are removed, and the impurity of the compounds such as sulfur-bearing, nitrogen, alkali metal also is eliminated to qualified index by purifier.For example, synthesis gas can be from gasification furnace or the partial oxidation reforming reactor of upstream.
The content of hydrogen is 70%-100% (volume ratio) in the side line hydrogen feed.Catalyst is cobalt-base catalyst, and main reactive metal is cobalt, and accelerative activator is one or more combinations in radium, platinum, ruthenium, lanthanum, zirconium, germanium, the titanium, and the carrier of catalyst is a kind of in aluminium oxide, silica, the titanium oxide or their combination; Different reactors can use the catalyst of different activities.Reactor is the multitube fixed bed, and operating pressure is 1.0-5.0MPa, and operating temperature is 160 ℃-300 ℃; The conversion ratio of carbon monoxide is 30%-70% in the single-stage reactor.
In conjunction with Fig. 1, based on said apparatus, feed and condition, its fischer-tropsch reaction process is as follows:
After the first order reactor feedstocks gas 10 that synthesis gas 7 and side line hydrogen make-up 9 are mixed enters first order fixed bed reactors 1, generate under catalyst action take linear paraffin as main compound and water, wherein water and light hydrocarbons exist with steam state and the part heavy hydrocarbon exists with liquid state.Liquid-vapor mixture and unreacted synthesis gas enter initial gross separation in the first order high- temperature separator 2,12 leave first order high-temperature separator 2 with liquid form take paraffin as major product, and tail gas 13 enters first order cold catch pot 3 with gaseous form and further separates in the middle of the first order.The temperature of first order cold catch pot 3 is controlled at 30 ℃ to 60 ℃ impelling water and most of light hydrocarbon to be condensed into liquid, and petrol and diesel oil is major product 14 with water 15 by different outlet first order cold catch pots 3.The second level reactor feedstocks gas 18 that the first order tail gas 16 that is comprised of unreacted synthesis gas and part gaseous hydrocarbons (being mainly C1-C4) mixes with side line hydrogen make-up 17 enters second level fixed bed reactors 4 and further reacts after preheating.The flow of side line hydrogen make-up 17 is according to specifically needing and can independently regulate, and its objective is that hydrogen-carbon ratio in the suitable raising 18 with the activity of the production capacity, particularly guard catalyst that improve second level reaction system, reduces its deactivation rate.
With the class of operation of first order reactor seemingly, synthesis gas reacts in the hydrocarbon products that obtains in the reaction system of the second level, paraffin is that major product 20 leaves second level high-temperature separator 5 with liquid form, petrol and diesel oil is that major product 22 and water 23 leave respectively second level cold catch pot 6 with liquid form, and the second level tail gas 24 that contains unreacted synthesis gas and part gaseous hydrocarbons then can enter third level reactor and continue to react, also can be used for the purposes of fuel and so on or directly send into the flare system discharged in burning.
Said process is particularly suitable for containing the synthesis gas of the inert gases such as nitrogen.In this environment, because effectively the concentration ratio of synthesis gas is lower, reaction heat on the per volume of catalyst is fewer, the existence of inert gas can help to remove the part heat, increase the heat transfer coefficient between beds and the reactor tube walls, thereby the temperature of effectively controlling beds raises.Simultaneously, but the dividing potential drop of inert gas cut back water, and this also is very helpful to the inactivation that prevents catalyst.
No matter be the catalyst that adopts iron-based or cobalt-based, water has negative effect to the activity of catalyst, is in particular in absolute dividing potential drop and the hydrogen water volume ratio of water in the reactor.When the dividing potential drop of water was in the certain limit, its impact belonged to the dynamics category, and water has just suppressed the activity of catalyst, can not cause the permanent deactivation of catalyst.But when the dividing potential drop of water surpassed this scope, the impact of water no longer belonged to reversible kinetic property, probably caused suddenly the induce reaction obstruction of device of the sintering of the structural fragmentation of collapse, catalyst granules of catalyst activity or catalyst.Similarly, when the hydrogen water volume ratio was lower than some numerical value, same phenomenon also can occur.But water is one of product of Fischer-Tropsch synthesis, and its existence is inevitable again, and the conversion ratio of synthesis gas is higher, and the absolute dividing potential drop of water is just higher, and the dividing potential drop of hydrogen is just lower, and the hydrogen water volume ratio is also lower, and they are consistent on the direction that affects of catalyst activity.The impact of water is especially obvious to the cobalt-base catalyst take aluminium oxide as carrier.In the present invention, the conversion rate control of single-stage synthesis gas such as 30%-70%, is preferably between the 40%-60% within the specific limits, to avoid water to the heavy damage effect of catalyst.Synthesis gas is through behind each reactor, all passing through condensation process takes out wherein hydrocarbon product and water, in order to avoid the product water of previous stage is brought into the next stage reactor, thereby can reduce the water content that enters next stage reactor synthesis gas, the life-span of extending catalyst.The present invention adopts a significance of plural serial stage reactor assembly to be, although the conversion ratio of single-stage reactor is not high, behind the plural serial stage, total conversion still can significantly be improved.If the conversion ratio of every A reactor all is 60%, so the summation of two-stage be exactly 84%, three grade summation be exactly 94%, can satisfy the needs of industrial practice fully.
In Fischer-Tropsch synthesis, the hydrogen carbon consumption of the hydrogen-carbon ratio in the synthesis gas and reaction is than being two important concepts.Concerning cobalt-base catalyst, the hydrogen carbon consumption of Fischer-Tropsch synthesis changes than the variation with product selectivity, but under the industrial operating mode of the overwhelming majority, the hydrogen carbon consumption is than generally being between the 2.0-2.2.If the hydrogen carbon consumption of the hydrogen-carbon ratio in the synthesis gas and reaction is than the same, hydrogen-carbon ratio will be the same with entrance in reactor outlet tail gas so, can't change, and this is a kind of ideal situation.If the hydrogen-carbon ratio of synthesis gas of coming self-gasifying device than the hydrogen carbon consumption of first order reactor than high, hydrogen-carbon ratio in the first order reactor tail gas will increase so, so that the second level and following reaction device all move in the environment of too high hydrogen-carbon ratio, the product selectivity variation has a strong impact on production capacity and the economy of device.If the hydrogen-carbon ratio of synthesis gas of coming self-gasifying device than the hydrogen carbon consumption of first order reactor than little, hydrogen-carbon ratio in the first order reactor tail gas will reduce so, so that the reaction rate of the second level and following reaction device descends, more seriously because the lower general who has surrendered of hydrogen water ratio increases the deactivation rate of catalyst, similarly affect production capacity and the economy of device.
An important feature of the present invention is at the entrance of every A reactor, all to be provided with independent hydrogen feed pipeline, so that the hydrogen-carbon ratio of timely conditioned reaction device charging synthesis gas.When the hydrogen-carbon ratio of the synthesis gas that comes self-gasifying device than the hydrogen carbon consumption of first order reactor than hour, this side line hydrogen can improve the hydrogen-carbon ratio in the reactor feed gas, the more important thing is the hydrogen-carbon ratio of replenishing the second level and following reaction device feeding gas, particularly prevent the rapid deactivation of catalyst to improve reaction rate.In addition, when first order reactor departs from former design conditions for a certain reason, such as improve reaction temperature for the inactivation of compensate for catalyst, the hydrogen carbon consumption of reactor is than being higher than original prediction so, can be adjusted to suitable ratio with the hydrogen-carbon ratio in the first order and the charging of following reaction device rapidly this moment by introducing a small amount of hydrogen, avoids hydrogen-carbon ratio excessively to hang down and cause unnecessary trouble.
The below provides several exemplary and nonrestrictive examples and helps explanation effect of the present invention.
Example 1
The fixed bed reactor system of three grades of series connection, three reactors all use the same cobalt-base catalyst, the product of each reactor outlet is through cooling and isolating hydrocarbon products and water, tail gas is sent to the next stage reactor, each reactor does not have the side line hydrogen make, and the operation operating mode of reactor as shown in Table 1.The hydrogen water ratio of second level reactor outlet is 0.87, under this operating mode, the unlikely rapid deactivation that causes catalyst still, but the hydrogen-carbon ratio of third level reactor outlet and hydrogen water drop to 0.18 and 0.1 than respectively, the deactivation rate of catalyst is obviously accelerated, and normal operation becomes very difficult.
Three grades in table one is without the circulating series reactor, without the side line hydrogen make
Example 2
The fixed bed reactor system of three grades of series connection, three reactors all use the same cobalt-base catalyst, the product of each reactor outlet is through cooling and isolating hydrocarbon products and water, tail gas is sent to the next stage reactor, first order reactor does not have the side line hydrogen make, second and the third level reactor side line hydrogen make is all arranged to improve the C/Hratio of feeding gas, the operation operating mode of reactor is as shown in Table 2.Owing to adopt the side line hydrogen make-up, the hydrogen water of the second level and third level reactor outlet is than 0.94 being 0.82 respectively, and catalyst does not have rapid deactivation owing to obtain the protection of q.s hydrogen.Compare with example one, in the situation of close total conversion, because the raising of hydrogen partial pressure causes the raising of catalyst aerodynamic efficiency, example two required hydrogen make-up consumptions are less than 2% of synthesis gas flow, but catalyst amount can save 25%.
Three grades in table two is without the circulating series reactor, band side line hydrogen make
Claims (8)
1. Fischer-Tropsch synthesizer is used for by the Fischer-Tropsch of the standby synthesis gas of normal air or oxygen-enriched air vaporizing system synthetic; It is characterized in that, comprise the reaction system of the loop-free at least two-stage series connection of tail gas, every first order reaction system comprises fixed bed reactors and the high-temperature separator that is linked in sequence and cold catch pot; The entrance of first order reaction system is provided with synthesis gas feed pipeline, and the cold catch pot of upper level connects the fixed bed reactors of next stage, and the fixed bed reactors of every first order reaction system are equipped with independent side line hydrogen feed pipeline.
2. the fischer-tropsch synthesis process based on the described Fischer-Tropsch synthesizer of claim 1 is characterized in that, comprising:
(1) supply with by normal air or the standby synthesis gas of oxygen-enriched air vaporizing system, wherein to add the shared volume ratio of carbon monoxide be the synthesis gas of 50%-80% to hydrogen;
(2) synthesis gas successively by the reaction system of described at least two-stage series connection, carries out respectively Fischer-Tropsch synthetic and separating hydrocarbons product and water without circularly;
In the process (2), according to the hydrogen-carbon ratio that enters in advance in this order reaction system gas, control the hydrogen supply of corresponding side line hydrogen feed pipeline, and the conversion ratio of controlling every first order reaction system is 30%-70%.
3. fischer-tropsch synthesis process according to claim 2, it is characterized in that: the volume ratio of hydrogen and carbon monoxide is 1.6-2.3 in the described synthesis gas.
4. fischer-tropsch synthesis process according to claim 3, it is characterized in that: the volume ratio of hydrogen and carbon monoxide is 1.8-2.1 in the described synthesis gas.
5. fischer-tropsch synthesis process according to claim 2 is characterized in that: the conversion ratio of controlling every first order reaction system is 40%-60%.
6. fischer-tropsch synthesis process according to claim 2, it is characterized in that: the volume content of hydrogen is 70%-100% in the feed of described side line hydrogen feed pipe.
7. fischer-tropsch synthesis process according to claim 2, it is characterized in that: the operating pressure of the fixed bed reactors of reaction systems at different levels is 1.0-5.0MPa, operating temperature is 160 ℃-300 ℃.
8. according to claim 2 to the described fischer-tropsch synthesis process of 7 any one, it is characterized in that: catalyst is cobalt-base catalyst, main reactive metal is cobalt, accelerative activator is one or more combinations in radium, platinum, ruthenium, lanthanum, zirconium, germanium, the titanium, and the carrier of catalyst is a kind of in aluminium oxide, silica, the titanium oxide or their combination.
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| CN102604677B (en) * | 2012-04-17 | 2013-01-30 | 太原理工大学 | High and low-temperature Fischer-Tropsch synthesis co-production technology |
| CN103773411B (en) * | 2012-10-25 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of method by hydrogen and carbon monoxide synthin |
| CN103773412B (en) * | 2012-10-25 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method adopting up-flow reactor synthin |
| CN103965939B (en) * | 2013-02-06 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of method by reaction of high order unit synthin |
| CN110021377B (en) * | 2017-10-31 | 2020-11-10 | 中国石油化工股份有限公司 | Method and device for predicting deactivation of hydrocracking catalyst and storage equipment |
| CN108384572B (en) * | 2018-03-12 | 2020-04-24 | 国家能源投资集团有限责任公司 | Method and system for adjusting hydrogen-carbon ratio of Fischer-Tropsch synthesis gas co-production hydrogen |
| CN110361499A (en) * | 2018-04-09 | 2019-10-22 | 国家能源投资集团有限责任公司 | The method of iron-base fischer-tropsch synthesis catalyst activity rating |
| EP4069638A1 (en) * | 2019-12-04 | 2022-10-12 | Topsoe A/S | Biogas conversion to synthesis gas for producing hydrocarbons |
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