CN100526273C - Method for integral production of liquid ammonia and methanol and/or dimethyl ether by using coke oven gas as raw material - Google Patents
Method for integral production of liquid ammonia and methanol and/or dimethyl ether by using coke oven gas as raw material Download PDFInfo
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- CN100526273C CN100526273C CNB2007101185999A CN200710118599A CN100526273C CN 100526273 C CN100526273 C CN 100526273C CN B2007101185999 A CNB2007101185999 A CN B2007101185999A CN 200710118599 A CN200710118599 A CN 200710118599A CN 100526273 C CN100526273 C CN 100526273C
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Abstract
The invention discloses an integrated liquid ammonia and menthol or dimethyl ether producing method with coking gas. The synthesis gas preparing applies with heat-exchanger type pure oxygen two-phase conversion process and is used to produce raw menthol firstly, the raw menthol can be used to produce menthol or dimethyl ether directly and the distillation process of raw menthol and the distillation process of dimethyl ether are associated so that menthol and dimethyl ether can proceed not only lonely but also uniquely; menthol synthesis off-gas and H2 by pressure-change absorption, separating and recovering are methanation-dealt so that H2, co and co2 are generated CH4 for synthesizing NH3 according to H2/N2=3: 1. The invention achieves ammonia-menthol-dimethyl ether integrated producing technique, which makes the heat energy recycle in the producing process, and achieves recycling of the effective element C and H in the coking gas.
Description
Technical field
The present invention relates to a kind of is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas.
Background technology
The raw material route of synthesis gas preparation is in the past between decades, experienced very big variation, before nineteen fifties, be raw material how with coal and coke, adopt fixed bed atmospheric pressure gas method to produce water-gas or semi-water gas, after the fifties, because a large amount of exploitations of Sweet natural gas and petroleum resources, more, can reduce the running cost of synthesis gas preparation and follow-up operation because Sweet natural gas is convenient to pipe-line transportation.Therefore, be the raw material production synthetic gas progressively just, thereby be born normal pressure Sweet natural gas partial oxidation method preparing synthetic gas with Sweet natural gas replacement coal and coke.Along with the tremendous development of metallurgical technology technology, and the high temperature alloy conversion tube (as HK-40, the solution of processing technology thereof HP-Nb), hydrocarbon gas steam under pressure conversion process has just replaced normal pressure partial oxidation technology.Up to now, transfer pressure is increased to 3.0～4.3MPa from normal pressure, and industrial scale also maximizes day by day, and single series synthetic ammonia scale is 1800MTPD, and single series methyl alcohol maximum-norm is 5000MTPD.Although with Sweet natural gas or oil is that raw material is produced the synthesis gas process technology and in decades considerable progress arranged in the past, be that the ratio of raw material production synthetic gas will have significantly and increase from now on the coal.This is that the storage capacity of solid fossil fuel is far more than liquid and gas because in the world in the energy structure, and particularly China is a deficency, few oil, the abundant relatively country of coal reserves, and coal accounts for more than 70% in disposable Energy production.Enter after 21st century, the coal chemical industry cause of China has entered a new developing period, particularly how production product after the coal deep processing and byproduct are fully utilized, effective element C in the hydrocarbons and H are carried out recycle, so that its influence to environment is dropped to minimum degree, be the key problem of the common concern of experts and scholars both at home and abroad in the present age.
China is maximum in the world coke production state, also is maximum coke export state, and coke(oven)gas output is very abundant, and according to the statistics made by the departments concerned, Chinese coke output can reach 300,000,000 tons in 2006.Therefore, coke(oven)gas output is roughly about 1200 billion cubic meters, if the coke(oven)gas that diffuses further is processed as synthetic gas, can produce about 5,900,000 tons of synthetic ammonia every year, perhaps can produce about 6,300,000 tons of methyl alcohol, and can and then be processed as about 4,370,000 tons of dme.If prepared synthetic gas is fully utilized, adopt methyl alcohol/dme/liquefied ammonia integrating technology to produce, just can realize the optimum target that world today's recycling economy is pursued, for the mankind create more high value, for environment is created more friendly atmosphere.
From the synthesis gas preparation technological angle, no matter traditional technology is the normal pressure partial oxidation or pressurizes continuous steam reforming technology, all be that secondary reformer is exported two sections reforming gas of high temperature, directly import waste heat boiler and produce high-parameters steam, and hydrocarbon gas steam reforming institute heat requirement has to supply with in the combustion of gaseous hydrocarbon materials according to anti-.If it is energy-conservation, its core is exactly to reduce the consumption of burning with hydrocarbons as far as possible, thereby realize the autothermal equilibrium of hydrocarbon gas steam reforming process or half autothermal equilibrium (the former transforms as LCA technology and heat exchange type oxygen-rich air, and the back is the conversion conversion process of connecting with heat exchange type as heat-exchanging type parallel).
For autothermal balance or the half autothermal balance that realizes hydrocarbon steam reforming conversion reaction process, since the eighties in last century, the hydrocarbon vapours Auto-thermal reforming process is just set about developing by external many renowned companies.Wherein realizing industrialized the earliest is the LCA technology of Britain ICI company, and its Ammonia Production scale is 350～450MTPD.This process using heat-exchanged reformer replaces traditional external-heat one-stage converter, and with the portion C H of one-stage converter
4The steam reforming load moves to thermo-efficiency near hundred-percent secondary reformer, adds than the desired N of stoichiometric ratio in secondary reformer
2Want many excess airs, to keep the autothermal balance of system, be used to simultaneously between the pipe of two sections reforming gas of high temperature at heat-exchanged reformer of secondary reformer and the pipe in the participation chemical reaction material between carry out heat exchange so that the required heat of hydrocarbons steam reforming reaction in the conversion tube to be provided.On the other hand, form (CO+H in order to satisfy ammonia synthesis gas
2)/N
2The requirement of=3:1, and be provided with transformation absorption (PSA) tripping device, to remove the excess nitrogen (N that brings into excess air
2), also remove CO simultaneously
2LCA technology is removing excessive N
2Process in, also cause certain amount of H
2Loss.In order to overcome this defective, adopt as Muscovite lattice sieve De-Nol nitrogen synthesis and to go here and there two sections conversions of oxygen-rich air after one section conversion of heat exchange type, thereby realized the purpose of system's autothermal equilibrium, there is not H again
2The loss problem just need be provided with a cover oxygenerator.
On LCA technology basis, succeeded in developing LCM technology in last century Mo ICI company again, be used to produce methyl methanol syngas, promptly in secondary reformer, add pure oxygen to replace excess air, meanwhile, in China, under the leader of the former chemical industry Room, Sichuan Province, at first succeed in developing the heat exchange type oxygen-rich air and transformed system ammonia synthesis gas technology, continue after Chengdu general engineering limited liability company succeeded in developing heat-exchanging type parallel again in succession and transform connect and transform system ammonia synthesis gas technology with heat exchange type, and two sections of heat exchange type pure oxygens transform system methyl methanol syngas and heat-exchanging type parallel and transform two sections conversions of string pure oxygen and make methyl methanol syngas technology.
The tempo of the methanol chemistry of China far lags behind abroad, and the extension of industrial chain also is very limited.As the dme of one of kind of methanol chemistry industrial chain, in the past Production By Sulfuric Acid Process technologies that adopt progressively change methanol gas phase dehydration catalyzed reaction technology (two-step approach) and have directly synthesized dme (single stage method) technology with synthetic gas now.The reaction of methyl alcohol sulfuric acid evaporation production dme is as follows:
H
2SO
4+CH
3OH＝CH
3HSO
4+H
2O
CH
3+SO
4+CH
3OH＝CH
3OCH
3+H
2SO
4
The methanol gas phase dehydration catalytic conversion reaction is as follows:
2CH
3OH＝CH
3OCH
3+H
2O
The reaction of direct synthesis of dimethyl ether from synthesis gas is as follows:
4H
2+2CO＝2CH
3OH
2CH
3OH＝CH
3OCH
3+H
2O
3CO+3H
2＝CH
3OCH
3+CO
2
CO+H
2O＝CO
2+H
2
Relatively seeing the following form of three kinds of production methods:
| The contrast project | The methanol liquid-phase dehydration method | The methanol gas phase dehydration method | The synthetic gas direct synthesis technique |
| Synthetic gas is formed | Desirable synthetic gas component H 2/CO＝2 | Be rich in the synthetic gas H of CO 2/CO＝1 | |
| The technology maturation degree | Large-scale device is abroad arranged, and domestic scale is less than normal, technology maturation | Large-scale device is abroad arranged, and domestic unit scale is less than normal, technology maturation | Domestic and international no large-scale device, technology is left to be desired |
| Flow process length | Flow process is slightly long, and the separation and the rectifying of dme are simple | Flow process is slightly long, and the separation and the rectifying of dme are simple | Flow process is slightly short, and the separation of dme and rectifying are complicated |
| Catalyzer | Sulfuric acid | Solid acid catalyst | Polyfunctional catalyst |
| Temperature of reaction ℃ | 130～160 | 200～240 | 250～300 |
| Reaction pressure MPa | Normal pressure | 0.1～0.5 | 2.5～6.0 |
| Transformation efficiency % | ～99 | <99 | 7 |
| DME selectivity % | >99 | <99 | >65 |
| Quality product qualification rate % | ≥99.6 | ≥99.9 | ～99 |
| Engineering risk | Engineering amplification risk is little | Engineering amplification risk is little | Engineering risk is big |
As can be seen from the above table, the methanol gas phase dehydration method is produced dme, the technology comparative maturity, and China's device of existing 100,000 tons/year at present is constructed and put into operation.
But, the above synthesis gas preparation methyl alcohol and process for preparing dimethyl ether, how all unresolved limited resources that makes is fully used, how making the tail gas (waste gas) that produces in the production process and waste liquid carry out problems such as recycle and solved, is major issue to be solved in the production process.
Summary of the invention
In order to overcome the above problems, the purpose of this invention is to provide a kind of is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, realizes resource and tail gas and waste liquid recycle, realizes combination producing, integrated management.
To achieve these goals, the invention provides a kind of is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, comprising:
A, the gas mixture that desulfurization coke(oven)gas and vapor mixing are obtained enter in the heat-exchanged reformer after preheater and process furnace preheating and transform, transform required heat energy by the high level heat indirect exchange gained from secondary reformer outlet synthetic gas in described heat-exchanged reformer, the reforming gas that comes out from described heat-exchanged reformer enters described secondary reformer and carries out CH
4Degree of depth conversion reaction, the degree of depth transforms required heat energy by oxygen in the described secondary reformer and H in described secondary reformer
2With part CH
4The reaction heat of being emitted that takes place to burn provides, and adds pure oxygen and steam simultaneously to keep system's thermal equilibrium in described secondary reformer, adds in described secondary reformer and is used to regulate synthetic gas H
2/ C ratio contain CO
2Gas; After finishing conversion reaction, described secondary reformer obtains high-temperature synthesis gas;
B, described high-temperature synthesis gas enter described preheater after supplying with the heat-exchanged reformer heat, again through waste heat recovery, be cooled to 30～50 ℃, and it is synthetic that the refrigerative synthetic gas is used for methyl alcohol, obtains thick methyl alcohol and methanol synthetic discharged gas delayed;
C, described methanol synthetic discharged gas delayed the separation through pressure-swing absorption apparatus (PSA) obtain containing CO
2Air-flow, contain H
2Air-flow and transformation fractionation by adsorption tail gas, the described CO that contains
2Air-flow is sent into described secondary reformer; The described H that contains
2Air-flow and N
2Production obtains liquefied ammonia and ammonia synthesis off-gas as liquefied ammonia raw materials for production gas in the gas mixing; Described transformation fractionation by adsorption tail gas and described ammonia synthesis off-gas are admitted to described process furnace and make fuel gas;
D, described thick methyl alcohol are used for incorporate methanol and dimethyl ether and select the production loop, obtain methyl alcohol, dme or methyl alcohol and dme;
Contain CO described in the steps A
2Gas bag is drawn together: from the described methanol synthetic discharged gas delayed CO that contains that obtains that separates through PSA
2Air-flow; CO from the recovery of process furnace stack gas
2Tail gas when selecting the production loop to produce dme from methanol and dimethyl ether.
When methanol and dimethyl ether described in the step D selects the production loop to be used to produce methyl alcohol, comprising: described thick methyl alcohol carries out rectifying through entering methanol rectifying system after the preheating, obtains high-precision methanol product.
When methanol and dimethyl ether described in the step D selects the production loop to be used to produce dme, comprise: described thick methyl alcohol enters the reaction of dme reaction unit and generates the thick dme of gas phase after heating up, the thick dme of described gas phase obtains dme and kettle base solution through condensation and rectifying; The non-condensable gas that the thick dme of described gas phase is separated simultaneously through condensation is sent into described secondary reformer after methanol wash, described kettle base solution is delivered to described methanol rectifying system and carried out rectifying and reclaim wherein methyl alcohol, and the methyl alcohol of recovery is sent into the dme reaction unit;
When methanol and dimethyl ether described in the step D selects the production loop to be used to produce methyl alcohol and dme, comprising: thick methyl alcohol is divided into two portions through the gas-phase methanol after the pre-rectifying, and a part directly obtains refined methanol; Another part enters the reaction of dme reaction unit and generates the thick dme of gas phase after heating up, the thick dme of described gas phase obtains dme and kettle base solution through condensation and rectifying; The non-condensable gas that the thick dme of described gas phase is separated simultaneously through condensation is sent into described secondary reformer after methanol wash, described kettle base solution is sent into described methanol rectifying system;
Extract wherein section H before coke(oven)gas of desulfurization described in the steps A and the described vapor mixing
2, this H
2With the described H that contains among the step C
2Air-flow mixes, and is used to produce synthetic ammonia.
Described in the steps A in the gas mixture mol ratio of total carbon be 0.8～4.0; It is 420～660 ℃ that described gas mixture is preheated the temperature that device and process furnace be preheating to, and pressure is 0.6～4.5MPa; Described gas mixture is 460～750 ℃ in heat-exchanged reformer exit temperature, CH
4Residual content is 5～18% (V
Do); Remaining CH in the synthetic gas of described secondary reformer exit
4Content is 0.3～0.9% (V
Do), temperature is 880～1050 ℃.
H in the described synthetic gas
2, CO and CO
2Gas composition meets the following conditions:
In the formula: f---ratio, no unit
H
2---the volume percent of hydrogen
CO
2---the volume percent of carbonic acid gas
The volume percent of CO---carbon monoxide
N described in the described step C
2The pure N that gas produces from air separation plant
2Gas is with H
2Ratio be 1:3.
The present invention not only realized the thermal cycling utilization in the production process, but also realized the recycle of effective element C and H in the coke(oven)gas, fundamentally solved preparing synthesis gas from coke oven gas H
2Too much, C reaches the problem that the tail gas (waste gas) that produces in the production process and waste liquid do not obtain recycle very little.The present invention has not only realized effective element C in the coke(oven)gas and the recycle of H, but also has realized the recycle of process heat in the production process, thereby reduces fuel gas consumption, reach energy-saving and cost-reducing, reduce investment and shorten the purpose of construction period,
Description of drawings
Fig. 1 is system and the schema that the present invention produces the method for liquefied ammonia and methyl alcohol and/or dme.
Embodiment
Embodiment 1:
With reference to figure 1, with the coke(oven)gas be the method for raw material integral production of liquid ammonia and methyl alcohol and dme concrete implement as follows:
A, coke(oven)gas be through wet desulphurization, sulphur removed obtain the coke(oven)gas 1 of sulphur content at 4～6ppm, boosts to 0.6～4.5MPa through overdraft then and obtain coke(oven)gas 2; Use synthetic gas 7 from waste heat boiler to be preheated to 300～380 ℃ and enter smart desulfurization, sulphur is removed to content obtains coke(oven)gas 4 less than 0.1PPm, allocate steam by a certain percentage in coke(oven)gas 4, controlling wherein, the mol ratio of total carbon is 0.8～4.0; The mixed gas of coke(oven)gas 4 and steam used to obtain temperature be that 420～660 ℃, pressure are the heating gas mixture 5 of 0.6～4.5MPa from entering the further preheating of process furnace after 7 preheatings of the synthetic gas between the heat-exchanged reformer pipe again, gas mixture 5 enters in the heat-exchanged reformer pipe, by means of catalyzer following reaction takes place at this:
CH
4+H
2O＝CO+3H
2—△Q
C
2H
6+2H
2O＝2CO+5H
2—△Q
CO+H
2O＝CO
2+H
2+△Q
In the formula: △ Q represents heat, because CH
4Deng the hydrocarbons steam reforming reaction is strong endothermic reaction, and institute's heat requirement is provided by secondary reformer outlet high-temperature synthesis gas 7;
In the formula: f---ratio, no unit;
H
2---the volume percent of hydrogen;
CO
2---the volume percent of carbonic acid gas;
The volume percent of CO---carbon monoxide.
Reaction in secondary reformer is:
H
2+0.5＝H
2O+△Q
Simultaneously with a small amount of CH
4Combustion reactions:
CH
4+O
2＝CO
2+2H
2O+△Q
Because a large amount of combustion reactions heat that above-mentioned two combustion reactionss are emitted rise to about 1400 ℃ the secondary reformer end flue temperature, are CH in the secondary reformer
4The degree of depth transforms essential heat is provided, the heat effect that in secondary reformer, produces, and it not only is the CH in the secondary reformer
4The degree of depth transforms provides heat, but also has created condition for the recycle of high level heat; Following reaction takes place in the secondary reformer beds:
CH
4+H
2O＝CO+3H
2—△Q
H
2O+CO＝CO
2+H
2+△Q
Along with the carrying out of reaction, the secondary reformer reaction bed temperature reduces from top to bottom gradually;
The tail gas 22 of discharging in the dme production process, from the methanol wash tower that the present invention adds separates H with methanol synthetic discharged gas delayed through PSA
2Rich CO behind the gas
2Gas 9 all is rich in H
2, CO, CO
2, C
2H
4, CH
4Deng, traditional technology all is this tail gas to be used for boiler or other process furnace is made fuel, because these two strands of air-flows join secondary reformer, the tail gas that methanol production and dme production are got rid of has been realized comprehensive utilization, become waste gas into producing unstripped gas, but also improved the quality of gained synthetic gas widely, thus make that the consumption of methanol production is reduced largely, because all contain CO in these two strands of air-flows
2, CO
2With CH
4Reduction reaction takes place and get CO+H
2, and these two kinds of active princlples that component all is a methanol production; That wherein reclaims from process furnace stack gas contains CO
2Gas 23 is directly to be disposed to atmosphere in traditional technology, can cause Greenhouse effect to environment, and stack gas reclaims CO
2After be disposed to atmosphere again, greatly improved environmental effect; In secondary reformer, finish degree of depth conversion and obtain synthetic gas 7;
B, secondary reformer export synthetic gas 7 temperature up to 880～1050 ℃, CH
4Content is 0.3～0.9% (V
Do), be introduced between the conversion tube pipe of heat-exchanged reformer, pass through the indirect heat exchange mode with coke(oven)gas that participates in chemical reaction in the pipe and mixture of steam, heat is offered heat-exchanged reformer to satisfy coke(oven)gas mixture of steam upgrading conversion reaction institute heat requirement in the heat-exchanged reformer conversion tube; Go out the synthetic gas between the heat-exchanged reformer conversion tube, contained high-order technology waste heat, be used for preheating coke(oven)gas/mixture of steam earlier, be used further to waste heat boiler and produce middle pressure steam (as process steam), all the other remaining in, low level waste heat (used heat) then is respectively applied for oiler feed and dme (or methyl alcohol) rectifying reboiler institute heat requirement, is used for the de-salted water that deaerator is gone in preheating at last; Synthetic gas is cooled to 30～50 ℃ through water-cooled then, isolate process condensate after, obtain synthetic gas 8, boost to the methyl alcohol synthesis pressure to carry out methyl alcohol synthetic synthetic gas 8 is compressed; The synthetic low-pressure process synthesis technique that adopts of methyl alcohol obtains thick methyl alcohol 11 and methanol synthetic discharged gas delayed 10 and unreacted synthetic gas 24, and unreacted synthetic gas 24 returns compression again, thereby constitutes methyl alcohol synthesis cycle loop.
Contain a large amount of H among the C, described methanol synthetic discharged gas delayed 10
2, being separated into three strands of air-flows through improvement transformation absorption (PSA), one is for containing H
2Air-flow 18, this contains H
2Air-flow is through the methanation refinement treatment, to remove with H
2The CO of the trace that the band of gas is gone into and CO
2, make CO+CO in this air-flow
2≤ 10PPm; And then press H
2/ N
2The ratio of=3:1 is allocated pure N into
2Gas 19, and boost to 8.0～22.0MPa and carry out ammonia synthesis, obtain liquefied ammonia and discharge ammonia synthesis off-gas 25, when increasing the turnout of synthetic ammonia, can from the desulfurization coke(oven)gas, extract section H
2Be used for and contain H
2Air-flow one is used from Ammonia Production; It two is rich CO
2Air-flow 9, this richness CO
2Air-flow 9 is sent into the unstripped gas of described secondary reformer as synthesis gas preparation, and it three is delivered to process furnace with ammonia synthesis off-gas 25 and make fuel, the CO that the burning back is produced for PSA tail gas 17
2Gas 23 returns to add the preparation unstripped gas of secondary reformer as synthetic gas 7 again.
Thick methyl alcohol 11 from the methanol synthesizing process discharge, after preheating, enter pre-rectifying tower and carry out pre-rectifying, and then the pressurization methanol rectifying tower, the methanol steam that comes out from cat head is divided into 12 and 12 ' two portions, wherein methanol steam 12 and then enter the normal pressure methanol rectifying tower and obtain product methyl alcohol; Methanol steam 12 ' enters dimethyl ether reactor after the methyl alcohol superheater is heated to the Dehydration of methanol temperature with the thick gas of dimethyl ether 13 of dimethyl ether reactor outlet high temperature, generate thick gas phase dme through the gas phase catalysis dehydration reaction; Go out the thick gas of dimethyl ether 13 of high temperature of dimethyl ether reactor, through the methyl alcohol superheater separate with condenser condenses and thick dme liquid 14, the tail gas 22 of the non-condensable gas 15 that condensation separation is come out after methanol wash reclaims wherein entrained dme send secondary reformer to make the unstripped gas of synthesis gas preparation.Thick dme liquid 14 gets the product dme through rectification process.Still liquid 16 send the raw materials for production of methyl alcohol compression rectification tower as methyl alcohol because of containing methyl alcohol at the bottom of the dme rectifying tower, makes dme production not have the sewage containing methanol discharging.Can be from the sewage containing methanol that methanol rectifying system is got rid of as oiler feed behind the middle pressure steam stripping, the hydrocarbon polymer that is come out by stripping from sewage containing methanol can participate in making synthetic gas with stripped vapor.
Embodiment 2:
With reference to figure 1, with the coke(oven)gas be the method for raw material integral production of liquid ammonia and methyl alcohol concrete implement as follows:
Steps A is identical with embodiment 1 with B, and difference only is to contain CO to the secondary reformer adding
2Air-flow be two strands: one is methanol synthetic discharged gas delayedly to separate H through PSA
2Rich CO behind the gas
2Gas 9, it two contains CO for what reclaim from process furnace stack gas
2Gas 23;
Contain a large amount of H among among C, the step B methanol synthetic discharged gas delayed 10
2, being separated into three strands of air-flows through improvement transformation absorption (PSA), one is for containing H
2Air-flow 18, this contains H
2Air-flow is through the methanation refinement treatment, to remove with H
2The CO of the trace that the band of gas is gone into and CO
2, make CO+CO in this air-flow
2≤ 10PPm; And then press H
2/ N
2The ratio of=3:1 is allocated pure N into
2Gas 19, and boost to 8.0～22.0MPa and carry out ammonia synthesis, obtain liquefied ammonia and discharge ammonia synthesis off-gas 25, when increasing the turnout of synthetic ammonia, can from the desulfurization coke(oven)gas, extract section H
2Be used for and contain H
2Air-flow one is used from Ammonia Production; It two is rich CO
2Air-flow 9, this richness CO
2Air-flow 9 is sent into the unstripped gas of described secondary reformer as synthesis gas preparation, its three be PSA tail gas 17 with ammonia synthesis off-gas 25, deliver to process furnace and make fuel, the CO that burning back is produced
2Gas 23 returns to add the preparation unstripped gas of secondary reformer as synthetic gas 7 again.
Thick methyl alcohol 11 from the methanol synthesizing process discharge, after preheating, enter pre-rectifying tower and carry out pre-rectifying, and then the pressurization methanol rectifying tower, close the outlet of methanol steam 12 ', the methanol steam 12 that only has out enters the normal pressure methanol rectifying tower and handles and obtain product methyl alcohol; Can be from the sewage containing methanol that methanol rectifying system is got rid of as oiler feed behind the middle pressure steam stripping, the hydrocarbon polymer that is come out by stripping from sewage containing methanol can participate in making synthetic gas with stripped vapor.
Embodiment 3:
With reference to figure 1, with the coke(oven)gas be the method for raw material integral production of liquid ammonia and dme concrete implement as follows:
Steps A is identical with embodiment 1 with B;
Contain a large amount of H among among C, the step B methanol synthetic discharged gas delayed 10
2, being separated into three strands of air-flows through improvement transformation absorption (PSA), one is for containing H
2Air-flow 18, this contains H
2Air-flow is through the methanation refinement treatment, to remove with H
2The CO of the trace that the band of gas is gone into and CO
2, make CO+CO in this air-flow
2≤ 10PPm; And then press H
2/ N
2The ratio of=3:1 is allocated pure N into
2Gas, and boost to 8.0～22.0MPa and carry out ammonia synthesis, obtain liquefied ammonia and discharge ammonia synthesis off-gas 25, when increasing the turnout of synthetic ammonia, can from the desulfurization coke(oven)gas, extract section H
2Be used for and contain H
2Air-flow one is used from Ammonia Production; It two is rich CO
2Air-flow 9, this richness CO
2Air-flow 9 is sent into the unstripped gas of described secondary reformer as synthesis gas preparation, and it three is delivered to process furnace with ammonia synthesis off-gas 25 and make fuel, the CO that the burning back is produced for PSA tail gas 17
2Gas 23 returns to add the preparation unstripped gas of secondary reformer as synthetic gas 7 again.
Thick methyl alcohol 11 from the methanol synthesizing process discharge, after preheating, enter pre-rectifying tower and carry out pre-rectifying, and then pressurization methanol rectifying tower, close the outlet of methanol steam 12, the methanol steam 12 ' that only has out enters dimethyl ether reactor after the methyl alcohol superheater is heated to the Dehydration of methanol temperature with the thick gas of dimethyl ether 13 of dimethyl ether reactor outlet high temperature, generate thick gas phase dme through the gas phase catalysis dehydration reaction; Go out the thick gas of dimethyl ether 13 of dimethyl ether reactor, through the methyl alcohol superheater separate with condenser condenses and thick dme liquid 14, the tail gas 22 of the non-condensable gas 15 that condensation separation is come out after methanol wash reclaims wherein entrained dme send secondary reformer to make the unstripped gas of synthesis gas preparation.Thick dme liquid 14 gets the product dme through rectification process.Still liquid 16 send the pressurization methanol rectifying tower to make the methanol production raw material because of containing methyl alcohol at the bottom of the dme rectifying tower.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail, will be understood by those skilled in the art that: still can make amendment or be equal to replacement the present invention with reference to the foregoing description; And do not break away from any modification or partial replacement of the spirit and scope of the present invention, all should contain within the scope of the invention.
Claims (7)
1, a kind of is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, it is characterized in that comprising:
A, the gas mixture that desulfurization coke(oven)gas and vapor mixing are obtained enter in the heat-exchanged reformer after preheater and process furnace preheating and transform, transform required heat energy by the high level heat indirect exchange gained from the secondary reformer synthetic gas in described heat-exchanged reformer, the reforming gas that comes out from described heat-exchanged reformer enters described secondary reformer and carries out CH
4Degree of depth conversion reaction, the degree of depth transforms required heat energy by oxygen in the described secondary reformer and H in described secondary reformer
2With part CH
4The reaction heat of being emitted that takes place to burn provides, and adds pure oxygen and steam simultaneously to keep system's thermal equilibrium in described secondary reformer, adds in described secondary reformer and is used to regulate synthetic gas H
2/ C ratio contain CO
2Gas; After finishing conversion reaction, described secondary reformer obtains high-temperature synthesis gas;
B, described high-temperature synthesis gas enter described preheater after supplying with the heat-exchanged reformer heat, again through waste heat recovery, be cooled to 30～50 ℃, and it is synthetic that the refrigerative synthetic gas is used for methyl alcohol, obtains thick methyl alcohol and methanol synthetic discharged gas delayed;
C, described methanol synthetic discharged gas delayed the separation through pressure-swing absorption apparatus obtain containing CO
2Air-flow, contain H
2Air-flow and transformation fractionation by adsorption tail gas, the described CO that contains
2Air-flow is sent into described secondary reformer; The described H that contains
2Air-flow and N
2Production obtains liquefied ammonia and ammonia synthesis off-gas as liquefied ammonia raw materials for production gas in the gas mixing; Described transformation fractionation by adsorption tail gas and described ammonia synthesis off-gas are admitted to described process furnace and make fuel gas;
D, described thick methyl alcohol are used for incorporate methanol and dimethyl ether and select the production loop, obtain methyl alcohol, dme or methyl alcohol and dme;
Wherein contain CO described in the steps A
2Gas bag is drawn together: from the described methanol synthetic discharged gas delayed CO that contains that obtains that separates through pressure-swing absorption apparatus
2Air-flow; CO from the recovery of process furnace stack gas
2Tail gas when selecting the production loop to produce dme from methanol and dimethyl ether.
2, according to claim 1 is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, when it is characterized in that methanol and dimethyl ether described in the step D selects the production loop to be used to produce methyl alcohol, comprise: described thick methyl alcohol carries out rectifying through entering methanol rectifying system after the preheating, obtains high-precision methanol product.
3, according to claim 1 is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, when it is characterized in that methanol and dimethyl ether described in the step D selects the production loop to be used to produce dme, comprise: described thick methyl alcohol enters the reaction of dme reaction unit and generates the thick dme of gas phase after heating up, the thick dme of described gas phase obtains dme and kettle base solution through condensation and rectifying; The non-condensable gas that the thick dme of described gas phase is separated simultaneously through condensation is sent into described secondary reformer after methanol wash, described kettle base solution is delivered to described methanol rectifying system and carried out rectifying and reclaim wherein methyl alcohol, and the methyl alcohol of recovery is sent into the dme reaction unit.
4, according to claim 1 is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, when it is characterized in that methanol and dimethyl ether described in the step D selects the production loop to be used to produce methyl alcohol and dme, comprise: thick methyl alcohol is divided into two portions through the gas-phase methanol after the pre-rectifying, and a part directly obtains refined methanol; Another part enters the reaction of dme reaction unit and generates the thick dme of gas phase, and the thick dme of described gas phase obtains dme and kettle base solution through condensation and rectifying; The non-condensable gas that the thick dme of described gas phase is separated simultaneously through condensation is sent into described secondary reformer after methanol wash, described kettle base solution is sent into described methanol rectifying system.
5, according to claim 1 is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, it is characterized in that extracting wherein section H before coke(oven)gas of desulfurization described in the steps A and the described vapor mixing
2, this H
2With the described H that contains among the step C
2Air-flow mixes, and is used to produce synthetic ammonia.
6, according to claim 1 is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, it is characterized in that the H in the described synthetic gas
2, CO and CO
2Gas composition meets the following conditions:
In the formula: f---ratio, no unit;
H
2---the volume percent of hydrogen;
CO
2---the volume percent of carbonic acid gas;
The volume percent of CO---carbon monoxide.
7, according to claim 1 is the method for raw material integral production of liquid ammonia and methyl alcohol and/or dme with the coke(oven)gas, it is characterized in that N described in the described step C
2The pure N that gas produces from air separation plant
2Gas is with H
2Ratio be 1:3.
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| CNB2007101185999A CN100526273C (en) | 2007-07-10 | 2007-07-10 | Method for integral production of liquid ammonia and methanol and/or dimethyl ether by using coke oven gas as raw material |
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| CNB2007101185999A CN100526273C (en) | 2007-07-10 | 2007-07-10 | Method for integral production of liquid ammonia and methanol and/or dimethyl ether by using coke oven gas as raw material |
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| CN101096331A CN101096331A (en) | 2008-01-02 |
| CN100526273C true CN100526273C (en) | 2009-08-12 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102191086B (en) * | 2010-03-16 | 2013-08-21 | 河南省化工设计院有限公司 | Integration device and method for coproducing carbon monoxide, methanol, hydrogen and refined synthetic gas in process of producing synthetic gas from coal |
| CN102180767A (en) * | 2011-03-10 | 2011-09-14 | 庞玉学 | Method and device for jointly producing methanol, ammonia and acetic acid by using coal and natural gas |
| WO2012130258A1 (en) * | 2011-03-29 | 2012-10-04 | Haldor Topsøe A/S | Method for the purification of raw gas |
| CN102211977A (en) * | 2011-04-07 | 2011-10-12 | 杨皓 | Process for producing synthetic ammonia and methanol by using coke oven gas and blast furnace gas |
| US9139492B2 (en) | 2011-09-15 | 2015-09-22 | Linde Aktiengesellschaft | Method for processing coke oven gas |
| CN102517108A (en) * | 2011-12-15 | 2012-06-27 | 西南化工研究设计院 | Technology for preparing liquefied natural gas and liquid ammonia by using coke oven gas |
| CN103275757B (en) * | 2013-05-23 | 2015-10-07 | 陕西煤业化工技术研究院有限责任公司 | A kind of method of oil gas coupling Poly-generation in Chemical Industry |
| CN105018164A (en) * | 2014-05-01 | 2015-11-04 | 北京蓝图工程设计有限公司 | Method for co-producing liquefied natural gas and urea by means of coke oven gas and converter gas |
| CN103936557B (en) * | 2014-05-12 | 2016-03-02 | 四川省达州钢铁集团有限责任公司 | A kind of technique utilizing ammonia tail gas increase yield of methanol processed |
| CN105732323B (en) * | 2016-02-18 | 2018-04-06 | 中国庆华能源集团有限公司 | The method for preparing the system of methanol with oven gas and methanol being prepared with the system |
| CN108707064B (en) * | 2018-06-28 | 2024-01-02 | 鹤壁宝发能源科技股份有限公司 | Production method for co-producing dimethyl ether by using blast furnace gas |
| CN110801797A (en) * | 2019-11-13 | 2020-02-18 | 唐山中润煤化工有限公司 | Nitrogen circulating temperature rise and fall system of methanol preparation device and application method thereof |
| CN113521968A (en) * | 2021-08-17 | 2021-10-22 | 安徽金禾实业股份有限公司 | Device and method for purifying alcohol post-gas in ammonia synthesis system |
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Assignee: The new Sichuan tonre Engineering Technology Co Ltd Assignor: Pang Yuxue Contract record no.: 2011510000134 Denomination of invention: Method for integral production of liquid ammonia and methanol and/or dimethyl ether by using coke oven gas as raw material Granted publication date: 20090812 License type: Exclusive License Open date: 20080102 Record date: 20110810 |