CN104230621A - Method for producing methane and co-producing low carbon alcohol from carbonaceous material - Google Patents
Method for producing methane and co-producing low carbon alcohol from carbonaceous material Download PDFInfo
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Abstract
A method for producing methane and co-producing low carbon alcohol from a carbonaceous material includes the steps: crude synthesis gas obtained after gasification of the carbonaceous material is purified to remove impurities in the crude synthesis gas, and thus purified synthesis gas is obtained; at least a portion of the purified synthesis gas and water are in contact with a mixed catalyst, a product obtained after contact is subjected to gas-liquid separation, and thus a gas product and a liquid product are obtained, wherein the mixed catalyst contains a water-gas shift catalyst and a catalyst for converting synthesis gas into low carbon alcohol; and a methanation gas raw material is in contact with a methanation catalyst, wherein the methanation gas raw material contains the gas product, and the H2/CO molar ratio in the methanation gas raw material is 2.8-3.5. According to the method, the methane can be produced and the low carbon alcohol can be co-produced, moreover, the load of water-gas shift in the process is effectively reduced, the energy consumption is saved, the utilization efficiency of carbon is improved, and furthermore, the method is performed directly on a methane production device of the prior art without increasing equipment.
Description
Technical field
The present invention relates to a kind of method of carbonaceous material indirect reformer, in particular, relate to the gasification of a kind of carbonaceous material for synthetic gas, Synthetic holography is the method for methane gas co-production low-carbon alcohol.
Background technology
Consider based on energy natural endowment and national energy security, coal conversion is domestic gas, transportation fuel, basic chemical industry raw material etc. by strategy that China just actively pushes forward " coal is for oil ".Wherein, coal preparing natural gas technology, is use low order brown coal through vaporizing system synthetic gas, is then converted into methane, is used as the process of the geseous fuel substituting conventional natural gas.
Coal preparing natural gas process efficiency is high, low, the technology relative maturity of water consumption, for exploitation western part of China remote districts coal, improve the standard of living of the people, decreasing pollution gaseous emission is significant.
The Technical Economy of coal process for producing natural process affects the important factor that this technology carries out.Big plain in u.s.a preparing methane from coal technique take brown coal as raw material, is 4000kcal/kg at brown coal calorific value, and when coal price is 150 yuan/t, add product conveying and city management expense, methane cost value is at 2.50 yuan/Nm
3left and right, at present, big plain in u.s.a engineering mainly relies on byproducts such as selling ammonia, sulphur, petroleum naphtha, tar, phenols to reduce the cost of methane, but fundamentally can not eliminate the puzzlement of economic factors to enterprise operation.
In addition, China's gas very unbalanced with gas, northern area gas consumption in winter is large, and it is few that non-heating season saves gas, and peaking problem is very serious.At present, the peak regulation means such as main employing underground natural gas storage, gas peak regulation generating or LNG, in addition, also can carry out peak regulation with coal preparing natural gas factory, that is coal preparing natural gas factory winter production Sweet natural gas, other seasons can a coproduction part liquid fuel, chemicals etc.
For solving peaking problem, Dalian Inst of Chemicophysics, Chinese Academy of Sciences proposes a series of catalyzer catalyzer as disclosed in CN102553600A, CN102553613A etc. producing methane co-production low-carbon alcohol for the synthesis of cyclostrophic, pointing out can coproduction liquid fuel when these catalyzer are produced methane for the synthesis of gas, can according to needs, by regulating reaction conditions thus obtaining the reaction product based on methane or the reaction product based on low-carbon alcohol.Although adopt this bifunctional catalyzer to efficiently solve peaking problem, before synthetic gas carries out methanation reaction, all need to regulate H through water gas shift reaction
2/ CO mol ratio, to be suitable for methanation reaction occurs, thereby increases energy consumption, has a large amount of CO
2discharge, reduces the service efficiency of carbon.In addition, the H needed for synthesis of low-carbon alcohol reaction
2/ CO mol ratio and the H needed for methanation reaction
2/ CO mol ratio is different, and therefore bifunctional catalyzer cannot at the H of its optimum
2carry out work under/CO mol ratio operational condition, cause catalyst efficiency lower.
Summary of the invention
The object of the invention is the above-mentioned deficiency in order to overcome prior art, providing that a kind of energy consumption is low, CO2 emissions is few and the method for being produced methane coproduction low-carbon alcohol by carbonaceous material of simple operation.
The present inventor researchs and analyses discovery, is the H in the clean synthetic gas that raw material process gasifies, purification obtains with carbon-rich materials such as coals
2/ CO mol ratio is lower, between 0.5-2.0.And clean synthetic gas prepares Sweet natural gas, require the H of clean synthetic gas
2/ CO mol ratio is advisable between 3.0-3.1.Therefore, for adjusting the H of clean synthetic gas
2/ CO mol ratio prepares Sweet natural gas to be suitable for methanation reaction, and clean synthetic gas has to pass through hydrosphere transformation operation and carries out H
2/ CO mol ratio adjusts, and by H
2/ CO mol ratio is H at the clean synthetic gas hydrosphere transformation of 0.5-2.0
2/ CO mol ratio is very large at the working load of the hydrosphere transformation operation of the gas of 3.0-3.1, and energy consumption is very high, and economy is low.
And the present inventor studies discovery, synthetic gas prepares the H in the tail gas of low-carbon alcohol
2/ CO mol ratio is generally higher than material synthesis gas, between 2.0-3.0, and by water gas shift catalyst be that the mixed catalyst obtained after the catalyst mix of low-carbon alcohol can realize hydrosphere transformation by Synthetic holography, again can synthesis of low-carbon alcohol, namely the water gas shift catalyst in mixed catalyst still can retain original hydrosphere transformation function, be that still to retain original be the function of low-carbon alcohol by Synthetic holography for the catalyzer of low-carbon alcohol by Synthetic holography, and the function of single catalyst can not be caused to have obviously disappear.Therefore, the present inventor imagines, for the clean synthetic gas that carbonaceous material is produced through gasification, purification, if to occur before methanation reaction first by clean synthetic gas and water gas shift catalyst be the catalyst mix of low-carbon alcohol by Synthetic holography after the mixed catalyst that obtains contact, can not only realize synthetic gas H
2the adjustment of/CO mol ratio, and a part of low-carbon alcohol can be produced, enrich product category, realize multiple coal-based product advantage complementary, effectively improve the economic benefit of coal preparing natural gas project and the ability of overall opposing risk.And because the tail gas of synthesis of low-carbon alcohol is compared to the H of material synthesis gas
2/ CO mol ratio increases, thus whole synthetic gas directly carried out hydrosphere transformation and then contacting the method for producing methane coproduction low-carbon alcohol with dual-function catalyst compared to prior art, achieve hydrosphere transformation adjustment H simultaneously
2/ CO mol ratio and coproduction low-carbon alcohol, thus make methanation catalyst at suitable H
2there is catalyzed reaction under/CO mol ratio, improve working efficiency.
Based on above-mentioned discovery, for realizing aforementioned object of the present invention, the invention provides a kind of method of being produced methane coproduction low-carbon alcohol by carbonaceous material, wherein, the method comprises: the crude synthesis gas that (1) obtains after being gasified by carbonaceous material carries out purifying to remove the impurity in described crude synthesis gas, obtains clean synthetic gas; (2) at least part of described clean synthesis G&W is contacted with mixed catalyst, and the product obtained after contact is carried out gas-liquid separation, obtain gaseous product and product liquid, described mixed catalyst contains water gas shift catalyst and is the catalyzer of low-carbon alcohol by Synthetic holography; (3) under methanation reaction condition, contacted by methanation gas raw material with methanation catalyst, described methanation gas raw material contains described gaseous product, the H in described methanation gas raw material
2the mol ratio of/CO is 2.8-3.5.
Methane co-production low-carbon alcohol can be produced according to method of the present invention, and effectively reduce the load of the hydrosphere transformation in process, save energy consumption, decrease CO in conversion process
2generation, improve the utilization ratio of carbon.Because it can be effectively energy-conservation while coproduction low-carbon alcohol, make it by winter of being particularly suitable for China because heating gas consumption is large, but not the few national conditions of heating season use gas, such as use it for as peak regulation means, compared to traditional traditional vigour peak means for load down of taking when avoiding non-heating season to save Sweet natural gas gas low ebb directly to stop work, method of the present invention can not produce the defects such as equipment damage is large, plant factor is low, operation fluctuation is large.
More specifically, compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
First, method provided by the invention, can to realize in same technical process by carbonaceous material through preparing methane by synthetic gas gas and low-carbon alcohol (being generally mixture of lower alcohols), enrich coal preparing natural gas product category, effectively can evade the market risk of the single existence of coal preparing natural gas product, simultaneously can according to produce market conditions of demand, by adjusting process condition, realize the coproduction of two kinds of products, and the two selectivity can be made adjustable in a big way, and do not affect the smooth operation of production equipment, and mixture of lower alcohols, no matter as high performance fuel or based on industrial chemicals, all there is wide market, therefore the economic benefit of process can be improved to a certain extent.
Secondly, method provided by the invention, can realize hydrosphere transformation and coproduction low-carbon alcohol, reduce the input of equipment and simplify operation in a reactor, and because the tail gas of coproduction low-carbon alcohol is compared to the H of material synthesis gas
2/ CO, than high, thus reduces the working load of hydrosphere transformation and acid gas removal body operation, is therefore conducive to the energy consumption and the CO that reduce technical process
2discharge, improve the utilization ratio of carbon.
3rd, method provided by the invention, that mixture of lower alcohols and gaseous product (methane) are carried out coproduction, because mixture of lower alcohols is liquid at normal temperatures and pressures, density is large, easily stores, carries out being separated easy realization with gas, thus this processing method can be realized without the need to increasing too much separating device, extra investment is little.
Method provided by the invention may be used for the technological process of various carbonaceous material (comprise coal but be not limited to coal) vaporizing system methane, and also may be used for has the carbonaceous material of market for natural gas demand to improve the utilization of synthesis tail gas through preparing low-carbon mixed alcohol by synthetic gas device.
Embodiment
The invention provides a kind of method of being produced methane coproduction low-carbon alcohol by carbonaceous material, wherein, the method comprises: the crude synthesis gas that (1) obtains after being gasified by carbonaceous material carries out purifying to remove the impurity in described crude synthesis gas, obtains clean synthetic gas; (2) at least part of described clean synthesis G&W is contacted with mixed catalyst, and the product obtained after contact is carried out gas-liquid separation, obtain gaseous product and product liquid, described mixed catalyst contains water gas shift catalyst and is the catalyzer of low-carbon alcohol by Synthetic holography; (3) under methanation reaction condition, contacted by methanation gas raw material with methanation catalyst, described methanation gas raw material contains described gaseous product, the H in described methanation gas raw material
2the mol ratio of/CO is 2.8-3.5.
According to method of the present invention, H in optimization methane oxidizing gases raw material
2/ CO mol ratio is 2.9-3.3.
In the present invention, the H in preferred described methanation gas raw material
2be 50-99 volume % with the total content of CO, specifically can adjust according to needs.
In the present invention, in concrete use procedure, can be first then load in reactor after the catalyst mix of low-carbon alcohol to use as beds by water gas shift catalyst with using Synthetic holography, also can not be the catalyst mix of low-carbon alcohol by water gas shift catalyst with by Synthetic holography, and use in two kinds of catalyzer separately direct layering in proportion or staggered layering loading reactor as beds.
According to method of the present invention, in the product after step (2) described contact, mainly comprise CO, H
2, CO
2and hydro carbons, carbon number that carbon number is less than 5 be the low-carbon alcohol of 1-6, unreacted synthetic gas, the carbon number gas hydro carbons, the carbon number that are less than 5 liquid hydrocarbon that is greater than 4, also comprise other byproducts of reaction such as organic oxygen-containing compound, water.
According to method of the present invention, step (2) described gaseous product is mainly containing CO, H
2, CO
2and the hydro carbons that carbon number is less than 5, described product liquid mainly containing carbon number be the low-carbon alcohol of 1-6, the carbon number hydro carbons, other organic oxygen-containing compounds and the water that are greater than 4.
Object of the present invention can be well realized according to preceding solution, in described mixed catalyst, water gas shift catalyst is wider with the content range of choices by Synthetic holography being the catalyzer of low-carbon alcohol, can adjust as required, such as when the less place of methane consumption is as south China or such as summer as typical in non-heating season time, when producing methane according to method of the present invention, because methane consumption is few, now can increase Synthetic holography is that the content of the catalyzer of low-carbon alcohol reduces the content of water gas shift catalyst with coproduction low-carbon alcohol as much as possible, thus on the one hand can coproduction low-carbon alcohol as much as possible, on the other hand, due to the H of the tail gas of synthol
2/ CO mol ratio is compared to the H of clean synthetic gas
2/ CO mol ratio is suitable for carrying out methanation reaction more, thus can effective energy efficient.For above-mentioned situation, general described mixed catalyst can contain water gas shift catalyst 60-90 % by weight, is the catalyzer 10-40 % by weight of low-carbon alcohol by Synthetic holography.
And when the place of methane large usage quantity is as northern China or such as winter as typical in heating season time, when producing methane according to method of the present invention, because methane consumption is large, now can reduce the load of the reaction of synthesis of low-carbon alcohol in step (2), such as can reduce Synthetic holography is that the content of the catalyzer of low-carbon alcohol increases the content of water gas shift catalyst with production methane as much as possible.For above-mentioned situation, general described mixed catalyst can contain the water gas shift catalyst of more than 60 % by weight, and less than 90 % by weight, for above-mentioned situation, general described mixed catalyst can containing the water gas shift catalyst of more than 10 % by weight, the catalyzer of the synthesis of low-carbon alcohol of less than 40 % by weight.
Based on foregoing description, in general preferred described mixed catalyst, water gas shift catalyst is 1-8:1 with being the weight ratio of low-carbon alcohol by Synthetic holography, is preferably 2-6:1.Then according to needing to regulate in above-mentioned scope.
Seen from the above description, method of the present invention effectively can realize coproduction and according to methane consumption size, can adjust flexibly, and effectively saved energy consumption in process, reduces CO
2generation, improve the utilization ratio of carbon.
According to method of the present invention, according to need can the consumption of clean synthetic gas described in set-up procedure (2), such as described for part clean synthesis G&W can be contacted with mixed catalyst, and remaining for another part clean synthetic gas is used for other purposes or carries out other process, and to make a living methanogenic method for main purpose of the present invention, contacted with mixed catalyst by whole described clean synthetic gas in preferred steps (2), now methanation gas raw material described in step (3) is only containing described gaseous product.
According to method of the present invention, in step (2), the range of choices of the condition of described contact is wider, the condition that can realize aforementioned claim all can realize object of the present invention, for the present invention, described in preferred steps (2), the condition of contact comprises: temperature is 150-500 DEG C, and pressure is 0.1-20MPa, and gas hourly space velocity is 100-50000h
-1, the mol ratio of water and carbon monoxide is 0.5-1.3:1.
In the present invention, the mol ratio of water and carbon monoxide refers to the mol ratio of carbon monoxide in water and clean synthetic gas.
According to method of the present invention, described water gas shift catalyst can be that the routine of this area is selected, such as can contain the Fe-Cr catalyzer of Fe and Cr for active ingredient element, in described Fe-Cr catalyzer with the content of oxide basis active ingredient for 60-95 % by weight, the content of auxiliary agent is 5-40 % by weight; And for example can contain the Cu-Zn catalyzer of Cu and Zn for active ingredient element, with oxide basis in described Cu-Zn catalyzer, the content of active ingredient is 45-90 % by weight, and the content of auxiliary agent is 10-55 % by weight; And for example can contain the Co-Mo catalyzer of Co and Mo for active ingredient element, with oxide basis in described Co-Mo catalyzer, the content of active ingredient is 60-85 % by weight, and the content of auxiliary agent is 15-40 % by weight.Wherein, described adjuvant component can be that the routine of this area is selected, and the present invention is not described in detail at this.
In the present invention, described is that the catalyzer of low-carbon alcohol can be selected for the routine of this area by Synthetic holography, such as can contain the Zn-Cr catalyzer of Zn and Cr for active ingredient element, with oxide basis in described Zn-Cr catalyzer, the content of active ingredient is generally 65-95 % by weight, the content of auxiliary agent is generally 5-35 % by weight, and adjuvant component element can be one or more in K, Li, Mg, Mn, Zr, Ce, La, Fe, Co, Pt and Pd; And for example can contain the Cu-Zn-Al catalyzer of Cu, Zn and Al for active ingredient element, 55-97 % by weight is generally with the content of oxide basis active ingredient in described Cu-Zn-Al catalyzer, the content of auxiliary agent is generally 3-45 % by weight, and adjuvant component element can be one or more in K, Li, Fe, Mn, Zr, Ce, La, Ni, Pt, Pd and Rh; And for example can contain the Cu-Co catalyzer of Cu and Co for active ingredient element, with oxide basis in described Cu-Co catalyzer, the content of active ingredient is generally 50-90 % by weight, the content of auxiliary agent is generally 10-50 % by weight, and adjuvant component element can be one or more of Cr, K, Li, Mn, Fe, Co, U, Rh, Pt, Zr, La and Nd; Can be such as MoS
2catalyzer, described MoS
2catalyzer refers to the oxide compound of molybdenum through sulfidizing, obtains the solid catalyst that S/Mo atomic ratio is 2; The Zn-Cr catalyzer of Zn, Cr can also be contained for active ingredient element, with oxide basis in described Zn-Cr catalyzer, the content of active ingredient is generally 75-99.5 % by weight, the content of auxiliary agent is generally 0.5-25 % by weight, and adjuvant component element can be one or more in K, Fe, Li, Al, Mn and La.
According to method of the present invention, described methanation reaction condition can be conventional selection, and for the present invention, preferred described methanation reaction condition comprises: pressure is 0.2-5MPa, and temperature is 250-750 DEG C, gas space velocity 100-20000h
-1.The present invention without particular requirement, can be fixed bed, moving-bed or fluidized-bed to the reactor of described methanation reaction, is preferably fixed bed or fluidized-bed.
According to method of the present invention, described methanation catalyst can be that the routine of this area is selected, and wherein, preferred described methanation catalyst is loaded catalyst, and in described loaded catalyst, active ingredient element is preferably Ni, carrier is preferably Al
2o
3.Described methanation catalyst can carry out chemical modification, the adjuvant component element that chemical modification adopts can be selected from La, Fe, Mg and Ce one or more.
According to method of the present invention, the method for described gas-liquid separation can adopt the various conventional gas-liquid separating method of prior art, and for the present invention, the method for preferred described gas-liquid separation is refrigerated separation, and the temperature of preferred described cooling is 5-40 DEG C.
According to method of the present invention, the method for described cooling can be direct contact cooling or indirect heat exchange cooling, and heat-eliminating medium can be water and/or petroleum fractions.
According to method of the present invention, preferred method of the present invention also comprises: before carrying out step (3), removes the carbonic acid gas in described methanation gas raw material, makes carbon dioxide content in methanation gas raw material lower than 2.0mol%.The method of carbon dioxide removal can be carried out with reference to prior art, and the present invention does not repeat them here.
According to method of the present invention, in described crude synthesis gas, impurity is generally containing tar, water vapour and S-contained substance etc.
According to method of the present invention, the method that the crude synthesis gas obtained after being gasified by carbonaceous material carries out purifying can be carried out with reference to prior art, it can be selected according to the dopant species in crude synthesis gas, impurity as previously mentioned in crude synthesis gas is generally containing tar, one or more in water vapour and S-contained substance, and when the impurity in described crude synthesis gas is simultaneously containing tar, when water vapour and S-contained substance, the step that the crude synthesis gas obtained after being gasified by carbonaceous material in step (1) carries out purifying generally comprises: cooled successively by described crude synthesis gas, detar, thick desulfurization, fine de-sulfur, and containing H in the clean synthetic gas obtained
220-40 % by mole, CO15-70 % by mole, CO
23-35 % by mole, CH
40-15 % by mole, and H
2s is less than 0.1 μ g/g.Wherein, the method for described cooling, detar, thick desulfurization, fine de-sulfur can be all the routine selection of this area, the present invention to this without particular requirement.
According to method of the present invention, described is conventional selection by the method that carbonaceous material gasifies, and generally comprises: under compressive reaction condition, contacted by carbonaceous material with vaporized chemical, described vaporized chemical is selected from one or more of air, oxygen and water vapour, is preferably the gas mixture of oxygen and water vapour.Described compressive reaction condition is conventional selection, generally comprises: temperature 450-2000 DEG C, pressure 0.1-20MPa.And according to needing, before by described carbonaceous material gasification, described carbonaceous material is carried out the pre-treatment such as drying, pulverizing, slurrying, preheating, melting, to this, those skilled in the art all know, and the present invention does not repeat them here.
According to the present invention, described gasification is generally carried out in vapourizing furnace, and described vapourizing furnace can select the operator scheme that fixed bed, moving-bed, fluidized-bed, air flow bed etc. are suitable, specifically can select according to the performance of carbonaceous material, the present invention, is not described in detail at this without particular requirement this.
According to method of the present invention, the kind of described carbonaceous material is conventional selection, including, but not limited to coal, be generally low-rank coal, be preferably in brown coal, long-flame coal, broken coal, fine coal, lump coal, caking coal, mud coal and coal water slurry one or more, for the present invention, preferred described carbonaceous material is brown coal and/or long-flame coal.
According to method of the present invention, preferred method of the present invention also comprises: step (2) gained product liquid is separated into liquid hydrocarbon, water etc. that low-carbon alcohol, carbon number that carbon number is less than 7 are greater than 4.Separating obtained water contains a certain amount of organism, sewage can be it can be used as to deliver to unit for treating water and process, then for device or arrange outward.
According to method of the present invention, preferred method of the present invention also comprises: the product after being contacted by step (3) gained carries out cooling to isolate moisture, obtains gas material, is separated described gas material, obtain the gas and the periodic off-gases that are rich in methane.According to method of the present invention, the method for described cooling can be direct contact cooling or indirect heat exchange cooling, and heat-eliminating medium can be water and/or petroleum fractions.According to method of the present invention, the method being separated described gas material can be carried out with reference to prior art, such as, can be separation by deep refrigeration or pressure swing adsorption process.
According to method of the present invention, described in be rich in methane gas can through mediation after or directly send into pipe network.Described periodic off-gases is generally containing low-carbon (LC) hydrocarbons, CO and CO
2in one or more, in order to improve the utilization ratio of carbon, reduce periodic off-gases and discharge the atmosphere polluting problem caused, described periodic off-gases can be returned step (3) and carry out methanation reaction to recycle, also described periodic off-gases can be returned step (1) to carry out gasifying to recycle, or described periodic off-gases is delivered to process furnace as gas alcohol.
The present invention is described further for the following examples, but not thereby limiting the invention.
Embodiment 1
The present embodiment is for illustration of method of being produced methane coproduction low-carbon alcohol by carbonaceous material provided by the invention.
Be that brown coal fragment (chemical group prejudice table 1) the oxygen/water steam of 5-50 millimeter is as vaporized chemical using granular size, gasification is crude synthesis gas, gained crude synthesis gas obtains clean synthetic gas (composition is in table 2), wherein (CO+H successively after overcooling, detar, thick desulfurization, fine de-sulfur operation
2) content is 63 volume %, H
2/ CO mol ratio is 1.59;
This clean synthetic gas is divided into G1 and G2 two strands, wherein G1 is delivered in synthesis reactor after heat exchange heats up, with mixed catalyst fixed bed contact reacts, beds is mixed by water gas shift catalyst and formate low-carbon alcohol catalyst, the two mass ratio is 3:1, and wherein, water gas shift catalyst is that (producer is Ke Li company to Co-Mo catalyzer, trade names QCS-01), consisting of of formate low-carbon alcohol catalyst: 40 % by weight CuO-37 % by weight Co
2o
3-21 % by weight MnO-2 % by weight K
2o; Compound reactor temperature in is 228 DEG C, and temperature out is 266 DEG C, and pressure is 6.25MPa, and gas space velocity is 5000h
-1, reacted product is cooled to 40 DEG C by indirect heat exchange, is divided into gas stream G
awith liquid stream L
a(part by weight is in table 3), gas stream G
ain (H
2+ CO) content be 47 volume %, the content of C1-C4 hydrocarbon is 15 volume %, H
2/ CO mol ratio is 2.95, liquid stream L
athe ratio of middle mixture of lower alcohols is 78 % by weight;
By G
acO
2be removed to 1.55 volume %, (H in gas stream
2+ CO) content be 65 volume %, then being heated up by further compression, heat exchange, deliver to methanator, take the content of element as the Ni/Al of 15 % by weight with nickel
2o
3catalyst exposure reacts, and temperature in is 304 DEG C, and temperature out is 461 DEG C, and pressure is 3.18MPa, and gas space velocity is 2500h
-1, the product be obtained by reacting cools through heat exchange, is cooled to 40 DEG C, isolates liquid water, and in the gaseous product obtained, the content of methane is 74.3 volume %.
Embodiment 2
The preparation of clean synthetic gas is identical with embodiment 1 with composition.This clean synthetic gas whole is divided into G1 and G2 two strands.Wherein, G1 delivers in synthesis reactor after heat exchange heats up, with mixed catalyst fixed bed contact reacts, beds is mixed by water gas shift catalyst and formate low-carbon alcohol catalyst, the two mass ratio is 4:1, and wherein, water gas shift catalyst is that (producer is Qingdao Intertrust, Inc. to Co-Mo catalyzer, trade names QDB-03), consisting of of formate low-carbon alcohol catalyst: 50 % by weight ZnO-47 % by weight Cr
2o
3-3 % by weight K
2o; Compound reactor temperature in is 305 DEG C, and temperature out is 342 DEG C, and pressure is 10.33MPa, and gas space velocity is 4500h
-1, reacted product is cooled to 40 DEG C by indirect heat exchange, is divided into gas stream G
awith liquid stream L
a(part by weight is in table 3), gas stream G
ain (H
2+ CO) content be 56 volume %, the content of C1-C4 hydrocarbon is 13 volume %, H
2/ CO mol ratio is 5.09, liquid stream L
athe ratio of middle mixture of lower alcohols is 92 % by weight;
By G2 and G
amixing, by the CO in gas mixture
2be removed to 1.48 volume %, now (H
2+ CO) content be 71 volume %, H
2/ CO mol ratio is 3.02, and by compressing further, heat exchange heats up, and then delivering to methanator, take the content of element as the Ni/Al of 15 % by weight with nickel
2o
3catalyst exposure reacts, and temperature in is 303 DEG C, and temperature out is 449 DEG C, and pressure is 3.94MPa, and gas space velocity is 2500h
-1, the product be obtained by reacting cools through heat exchange, is cooled to 40 DEG C and isolates liquid water, and in the gaseous product obtained, the content of methane is 90.2 volume %.
Comparative example 1
The preparation of clean synthetic gas is identical with embodiment 1 with composition.The clean synthetic gas obtained directly is delivered to hydrosphere transformation unit, catalyzer is that (producer is Qingdao Intertrust, Inc. to Co-Mo catalyzer, trade mark QDB-03), reactor inlet temperature is 250-260 DEG C, temperature out is 283 DEG C, water/carbon monoxide mole ratios is 1.3:1, and pressure is 3.8MPa, obtains hydrosphere transformation gas.By CO wherein
2be removed to 1.71 volume %, (H
2+ CO) content be 86 volume %, H
2/ CO mol ratio is 3.03, and by compressing further, heat exchange heats up, and then delivering to methanator, take the content of element as the Ni/Al of 15 % by weight with nickel
2o
3catalyst exposure reacts, and temperature in is 304 DEG C, and temperature out is 461 DEG C, and pressure is 3.03MPa, and gas space velocity is 2500h
-1, the product be obtained by reacting cools through heat exchange, is cooled to 40 DEG C and isolates liquid water, and in the gaseous product obtained, the content of methane is 95.3 volume %.
Table 1
Table 2
| Clean synthetic gas main ingredient | (% by mole) |
| H 2 | 38.7 |
| CO | 24.3 |
| CO 2 | 26.5 |
| CH 4 | 8.3 |
| N 2 | 1.2 |
| AR | 0.6 |
| C2 +Hydrocarbon | 0.5 |
Table 3
Note:
(1) total amount of liquid=G1 × L
a/ 100
(2) total total amount of liquid of gas volume=100%-
(3) total hydrosphere transformation load reduction (reducing Δ WGS in CO2 emissions), is calculated as:
Wherein,
Y
0---CO+H in unstripped gas gas
2percent by volume, %;
R
0---H in unstripped gas gas
2/ CO mol ratio;
R
3---H in methanation unstripped gas
2/ CO mol ratio.
(4) CO
2relative emission changes delta RCE is calculated as:
From the result of embodiment and comparative example, be compared to comparative example 1, adopt method provided by the invention, can by brown coal through clean synthetic gas co-production of methane gas and low-carbon alcohol.Compared to comparative example, according to the working method of embodiment 1, embodiment 2, there is methanation reaction after reaction end gas is mixed with remaining clean synthetic gas, hydrosphere transformation load can be reduced on the whole and be respectively 17.2%, 17.0%, for the CH of production unit volume
4, CO
2quantity discharged reduce 1.7%, 1.6% respectively.Visible, method of the present invention can realize the coproduction of methane gas and low-carbon alcohol, not only total in process CO
2quantity discharged reduces, and production unit volume CH
4cO
2quantity discharged also reduces to some extent, illustrates that the present invention effectively can also improve the utilization ratio of carbon, reduces the discharge of process carbon.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (11)
1. produced a method for methane coproduction low-carbon alcohol by carbonaceous material, it is characterized in that, the method comprises:
(1) crude synthesis gas obtained after being gasified by carbonaceous material carries out purifying to remove the impurity in described crude synthesis gas;
(2) at least part of described clean synthesis G&W is contacted with mixed catalyst, and the product obtained after contact is carried out gas-liquid separation, obtain gaseous product and product liquid, described mixed catalyst contains water gas shift catalyst and is the catalyzer of low-carbon alcohol by Synthetic holography;
(3) under methanation reaction condition, contacted by methanation gas raw material with methanation catalyst, described methanation gas raw material contains described gaseous product, the H in described methanation gas raw material
2the mol ratio of/CO is 2.8-3.5.
2. method according to claim 1, wherein, in step (2), in described mixed catalyst, water gas shift catalyst is 1-8:1 with being the weight ratio of the catalyzer of low-carbon alcohol by Synthetic holography.
3. method according to claim 1 and 2, wherein, described be the catalyzer of low-carbon alcohol by Synthetic holography is Zn-Cr catalyzer, Cu-Zn-Al catalyzer, Cu-Co catalyzer and MoS
2one or more in catalyzer.
4. method according to claim 1 and 2, wherein, described water gas shift catalyst is one or more in Fe-Cr catalyzer, Cu-Zn catalyzer and Co-Mo catalyzer.
5. method according to claim 1 and 2, wherein, in step (2), contacts whole described clean synthetic gas with mixed catalyst; In step (3), described methanation gas raw material is described gaseous product.
6. method according to claim 1 and 2, wherein, in step (2), the condition of described contact comprises: temperature is 150-500 DEG C, and pressure is 0.1-20MPa, and gas hourly space velocity is 100-50000h
-1, the mol ratio of water and carbon monoxide is 0.5-1.3:1.
7. method according to claim 1 and 2, wherein, in step (2), the method for described gas-liquid separation is cooling, and the temperature of described cooling is 5-40 DEG C.
8. method according to claim 1 and 2, wherein, in step (3), the H in described methanation gas raw material
2be 50-99 volume % with the total amount of CO.
9. method according to claim 1 and 2, wherein, in step (3), described methanation reaction condition comprises: pressure is 0.2-5MPa, and temperature is 250-750 DEG C, gas space velocity 100-20000h
-1.
10. method according to claim 1 and 2, wherein, in step (1), the step that after being gasified by carbonaceous material, the crude synthesis gas that obtains carries out purifying comprises: described crude synthesis gas is carried out successively cool, detar, thick desulfurization and fine de-sulfur, and containing H in the clean synthetic gas obtained
220-40 % by mole, CO15-70 % by mole, CO
23-35 % by mole, CH
40-15 % by mole, and H
2s is less than 0.1 μ g/g.
11. methods according to claim 1 and 2, wherein, described carbonaceous material is brown coal and/or long-flame coal.
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| US20090259076A1 (en) * | 2008-04-09 | 2009-10-15 | Simmons Wayne W | Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology |
| CN101892103A (en) * | 2009-04-22 | 2010-11-24 | 通用电气公司 | Be used to produce the method and apparatus of substitute natural gas |
| CN101979468A (en) * | 2010-11-11 | 2011-02-23 | 中国科学院山西煤炭化学研究所 | Low-carbon emission Fischer-Tropsch synthesis reaction process |
| CN102531819A (en) * | 2010-12-30 | 2012-07-04 | 中国科学院大连化学物理研究所 | Method for preparing methane and methanol by using synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090259076A1 (en) * | 2008-04-09 | 2009-10-15 | Simmons Wayne W | Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology |
| CN102056657A (en) * | 2008-04-09 | 2011-05-11 | 万罗赛斯公司 | Process for converting a carbonaceous material to methane, methanol and/or dimethyl ether using microchannel process technology |
| CN101892103A (en) * | 2009-04-22 | 2010-11-24 | 通用电气公司 | Be used to produce the method and apparatus of substitute natural gas |
| CN101979468A (en) * | 2010-11-11 | 2011-02-23 | 中国科学院山西煤炭化学研究所 | Low-carbon emission Fischer-Tropsch synthesis reaction process |
| CN102531819A (en) * | 2010-12-30 | 2012-07-04 | 中国科学院大连化学物理研究所 | Method for preparing methane and methanol by using synthesis gas |
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