CN105111107B - A kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide - Google Patents
A kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide Download PDFInfo
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- CN105111107B CN105111107B CN201510466356.9A CN201510466356A CN105111107B CN 105111107 B CN105111107 B CN 105111107B CN 201510466356 A CN201510466356 A CN 201510466356A CN 105111107 B CN105111107 B CN 105111107B
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Abstract
A kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide includes coal gas unit, synthesis gas prepares clean unit, higher alcohols synthesis and separative element, the main urea synthesizing unit of ammonia synthesis unit.The present invention have technique it is simple, cost is low, can large-scale the advantages of.
Description
Technical field
The present invention relates to a kind of technique of coal low-carbon alcohols, and in particular to one kind is by coal through low carbon alcohol by synthetic gas and dioxy
Change carbon comprehensive utilization coproduction urea and LNG technique.
Background technology
Low-carbon alcohols are often referred to C1~C5 alcohol-based mixtures.Application prospect is quite varied：1st, as alternative fuel, although it is hot
It is worth relatively low, but it is abundant to burn, and the CO, NOx, the hydro carbons etc. that are discharged in burning are less, are environmentally compatible fuels；2nd, as fuel
Additive.Because there is the problems such as storage, transport in used methyl tertiary-butyl ether, with the progressive meeting eventually of science and technology
Disabled, this provides opportunity for the exploitation of low-carbon alcohols.It is explosion-proof, anti-seismic performance is good and low-carbon alcohols octane number is higher.Simultaneously
Low-carbon alcohols are of great value as chemical products and large Chemical Manufacture raw material.At present, Global Oil resource increasingly consumes, energy
Source safety problem is increasingly severe, and the research and development of new energy system is extremely urgent.Synthesis gas chemical industry is current energy
The focus in work field, wherein be combined to synthesis gas via coal gas, then by synthesis gas catalytic hydrogenation synthesis of low-carbon alcohol it is that research is more
One of problem.
As at the beginning of synthesizing low-carbon alcohol from synthetic gas technology starts from last century, the oil crisis of the 1970s so that various countries
Substantial amounts of research is done in terms of synthesizing low-carbon alcohol from synthetic gas, the technology path of domestic and international higher alcohols synthesis mainly has:U.S. road
The Sygmol techniques that chemical company and union carbide corporation develop jointly；The IFP techniques of France Petroleum Institute；Lurgi exploitations
Octamix techniques；The MAS techniques that Italian Snam and Denmark Topse is developed jointly.In above-mentioned technique, MAS techniques are most ripe,
But more advanced at present is octamix techniques and Sygmol techniques, and both technological reaction mild conditions, alcohol selectivity is high, slightly
Product water content is low.And the Auditory steady-state responses of Octamix techniques are significantly less than Sygmol techniques, this is favourable to improving process thermal efficiency
's.And sulfur content is more than 100 times of Octamix techniques in the unstripped gas that Sygmol process catalysts allow, therefore it is expected province
Desulfurization process is removed, the exploitation and popularization of the sulfur resistant catalyst, not only to mixed alcohol technique, and methanol industry may also be produced
Tremendous influence.Not only C2+ alcohol contents are high in Sygmol process products, and the content of ethanol and propyl alcohol accounts for 50%.Ethanol
It is industrial chemicals in short supply at present with propyl alcohol, and it is expensive, therefore from the point of view of product structure, Sygmol techniques are more beneficial for industry
Utilize.
In above-mentioned technique, MAS techniques are most ripe, but more advanced at present is octamix techniques and Sygmol techniques, and this two
Kind technological reaction mild condition, alcohol selectivity is high, and crude product water content is low.And the Auditory steady-state responses of Octamix techniques are significantly less than
Sygmol techniques, this is favourable to improving process thermal efficiency.And Sygmol techniques use sulfur resistant catalyst, therefore it is expected to save
Desulfurization process, the exploitation and popularization of the sulfur resistant catalyst, not only to mixed alcohol technique, and methanol industry may also be produced huge
Big influence.Not only C2+ alcohol contents are high in Sygmol process products, and the content of ethanol and propyl alcohol accounts for 50%.Ethanol and
Propyl alcohol is industrial chemicals in short supply at present, and expensive, therefore from the point of view of product structure, Sygmol techniques are more beneficial for industrial profit
With.But all there is the problem of all not abundant enough to the components utilising of synthesis gas in these techniques.
Patent CN202040470A is used for the method and a kind of synthesis gas of patent CN101891588A of low carbon alcohol by synthetic gas
The method of synthesis of low-carbon alcohol, all disclose the method for preparing catalyst of a kind of synthesis of low-carbon alcohol and feasible on synthesis of low-carbon alcohol
Property, industrialized application is not involved with completely.But also it is only to rest on laboratory bench scale, the amplification of its engineering also has very
Big unpredictability, it is far away from industrial applications.
A kind of methods by synthesis gas continuous production low-carbon alcohols of patent CN101805242A, disclose a kind of synthesis gas production
The technique of low-carbon alcohols and alkene hydration generation correspondent alcohol, is a kind of continuous production processes, is in synthesis gas system the characteristics of the invention
The reaction of alkene hydration generation correspondent alcohol, unreacted synthesis gas and light alkene closed cycle drop are added after low-carbon alcohols reaction
Low energy consumption, improve the yield of synthesis gas utilization rate and alcohol.But the target product conversion ratio of this method is not high, exhaust gas component
Complexity, and utilization is only synthesized again to the alkene in tail gas, it is seen that it is substantially relatively low to the utilization rate of tail gas, and this method
Obtained fusel it is excessive, the selectivity of low-carbon alcohols is not high.
A kind of technologies of co-producing low-carbon alcohol and natural gas by coal synthesis gas of patent CN101735008A, disclosing one kind will be low
The technology that carbon alcohol synthesis technique and methanation process are combined, including gas purification, synthesis collection, tail gas separation and the first of alcohol
Several parts such as alkanisation, a tail gas part for synthesis of low-carbon alcohol are recycled back to higher alcohols synthesis device, another part synthesizing methane.Patent
A kind of sulfur tolerant catalyzing process of preparing low carbon alcohol from synthesis gas and co-producing natural gas of CN101735009A, disclose a kind of by sulfur-resistant low-carbon
Alcohol synthesis technique is combined technique with methanation in presence of sulfur production natural gas process, and synthesis gas can carry out low-carbon without fine de-sulfur
Alcohol synthesis reaction, a tail gas part are recycled back to higher alcohols synthesis reactor, and another part enters methanation device synthesizing methane, real
Show the Sulfur tolerance and Poly-generation of whole flow process, improve the economy of device to a certain extent.But both technologies are all deposited
It is not high in low-carbon alcohols yield, and low-carbon alcohols do not separate, the shortcomings that high energy consumption.Its Patent CN101735009A works as synthesis gas
Middle CH4>Elder generation's pressure-variable adsorption methane when 5%, then synthesis of low-carbon alcohol, as CH4 in synthesis gas<Elder generation's synthesis of low-carbon alcohol when 5%, then transformation
Adsorbed methane, synthesis of low-carbon alcohol.This method is difficult really to realize in the industrial production, it is therefore apparent that both techniques are present
Flow is cumbersome, and operational management is complicated, is unsuitable for industrialization promotion.
The content of the invention
It is an object of the invention to provide a kind of technique is simple, cost is low, can large-scale production coal low-carbon alcohols and two
Carbonoxide comprehensively utilizes coproduction urea and LNG process system.
The present invention is that colm prepares low-carbon alcohols by synthesis gas and produces remaining methane, Utilization of Carbon Dioxide
The technique of urea and LNG.This technique realizes the multistage coproduction of coal, and classified utilization, whole flow process is without greenhouse gas emission, energy-conservation
Water saving, technological process is simple, close to zero-emission, realizes the clean utilization of coal.
This technique can be divided into synthesis gas by function and prepare clean unit, higher alcohols synthesis and separative element, urea synthesizing
Unit
The technique of a kind of coal low-carbon alcohols and Utilization of Carbon Dioxide provided by the invention specifically includes following steps：
(1) raw coal, the oxygen from space division and vapor obtain raw gas through coal gas unit style, and raw gas becomes through resistant to sulfur
Change, low-temp methanol is washed and the obtained pure synthesis gas for meeting higher alcohols synthesis after methane separation；Low-temp methanol washes the H isolated2S
Concentrated gas removes sulfur recovery, CO2Urea synthesizing is removed, LNG product is made in the methane that methane separation obtains；
(2) low-carbon alcohols mix products, low-carbon alcohols mix products are made through higher alcohols synthesis catalyst in the synthesis gas after purifying
After knockout tower, methanol, ethanol, propyl alcohol and butanol product are isolated；
(3) higher alcohols synthesis periodic off-gases are through UF membrane (PSA), CO, CO of separation2Return to low-temp methanol to wash, the H of separation2With
N from space division2Ammonia must be synthesized into synthesis ammonia synthesis unit style；
(4) low-temp methanol washes the CO isolated2Mixed with the synthesis ammonia of step (3) and carry out urea synthesizing, obtain synthesis urine
Element.
Coal gas as described above uses to pressurize suitable for low-quality lignite (water content 20%-30%) and bituminous coal broken coal
Gasification furnace or slack coal slag gasifier (BGL), gasification temperature is at 1000-1450 DEG C, vapor pressure 4.0-6.0MPa.
The remarkable advantage of the gasification technology is：
1. being adapted to the low-quality coal gasification that water content is big, ash is high, about 8-12% methane is rich in raw gas,
2. rate of gasification is high, the intensity of gasification is big, and crushed coal pressure gasifying technology vapor pressure is big, and gasification temperature is high, therefore gasifies
Reaction speed is high, and the intensity of gasification greatly improves, and compared with other gasification technologies, the cold gas efficiency of crushed coal pressure gasifying reaches
90%, efficiency of carbon con version>995%, more than 93% energy be converted into can trans-utilization fuel, and water-coal-slurry is under the same terms
78% or so, shell gasification furnace is 82% or so.
3. oxygen consumption is low, for vapour/oxygen than low, steam consumption is low：
4. technology maturation, stable, crushed coal pressure gasifying technology has domesticized and in Datang gram flag and Xinjiang celebrating China
Successful application more than 70 covers, the design for gasification furnace, and manufacture and the operational control country all have wide experience, and generally speaking broken coal adds
Calming the anger furnace technology is simple, and auxiliary equipment is few, and reliability is high, stable, flexible adjustment.
Conversion as described above is using the Co-Mo sulfur-resistant transformation catalyst medium temperature sulphur-resistant conversion works with high hydrolysis function
Skill, conversion pressure are 2.5-4.4MPa, and transformation temperature is 220-450 DEG C, and water/gas mol ratio is between 0.25-0.40, with dry
It is 3000-5000h that gas, which calculates volume space velocity,-1。
The described Co-Mo sulfur-resistant transformation catalysts with high hydrolysis function mainly include following several：
World Catalyst：The SSK type catalyst of Top of Denmark rope, the K8-11 type catalyst of BASF Corp. of Germany, Japan are emerging
The C113 type catalyst of Co., Ltd. is produced, the C25-2-02 catalyst of UCI companies of the U.S., above-mentioned four kinds of catalyst are all once in state
Applied in interior industry, it is especially the most successful with the K8-11 catalyst of BASF AG, but in recent years, with the progress of domestic technique,
Multiple serial sulfur-resistant transformation catalysts have successfully been developed, and its various performance has been fully achieved or better than World Catalyst.
Domestic catalyst：The QDB series sulfur-resistant transformation catalysts of Qingdao Lian Xin chemical industry Co., Ltd production, wherein especially
Using QDB-04 types catalyst to be best, it not only has higher activity and stability, and can be with a certain degree of suppression first
The side reactions such as alkanisation.The QCS series sulfur-resistant transformation catalysts of Ke Li chemical companies of Qilu Petrochemical research institute production, have intensity
Height, low temperature active with great difficulty regenerate the advantages that, representative is QCS-04 type catalyst；The exploitation of Hubei chemical research institute
The sulfur-resistant transformation catalyst of EB series, the good catalyst activity, long lifespan, easily regeneration, it is widely used.
It is low-temp methanol washing process there is provided prewashing and regenerative system that low-temp methanol as described above, which is washed, operation temperature
For -35 to -55 DEG C, operating pressure 2.0-6.0MPa's, H in the synthesis gas after low-temp methanol is washed2S<0.1ppm,CO2<
20ppm,
Due to low-quality coal complicated component, the coal gas tapping temperature through crushed coal pressure gasifying is low, raw gas complicated component.Its
Gas component includes CO, H2、CO2、CH4、H2S, organic sulfur, C2H4、C2H6、C3H8、C4H10、HCN、N2, Ar and tar, fat
Sour, single phenol, multiple phenol, naphtha, oil etc..CO, H are removed in these components2Active principle and CH4、N2, Ar and hydro carbons category inertia
Outside gas, remaining all components includes CO2All it is the objectionable impurities for needing to remove with sulfide, it is seen that it purifies the difficult of task
It is huge.Current various gas purifying techniques are made a general survey of, this person with heavy responsibilities's non-cryogenic methanol can be taken on washes and do not belong to.Because only low temperature first
Alcohol cleanization just all can neatly remove various harmful components, such as CO in same device2、H2S、COS、C4H4S、
HCN、NH3、H2O、C2Above hydro carbons (including light oil, aromatic hydrocarbon, naphtha, alkene and colloid etc.) and other carbonyl compounds
Thing etc., and other any purification techniques can not all accomplish.Other crushed coal pressure gasifying raw gas pressure is higher, CO in gas2、H2S
Partial pressure is of a relatively high, so being advantageous for playing the characteristic that low-temp methanol washes Physical Absorption in itself.In addition, low-temp methanol is washed
Technique also has the advantages of following various notable compared with other purification techniques：
● absorbability is strong, and solution internal circulating load is small
● methanol solvate is cheap and easy to get, and regeneration energy consumption is low
● gas purification degree is high
● solvent heat endurance and chemical stability are good, and solvent is non-degradable, non-foaming, and equipment is not corroded
● solution viscosity is small, is advantageous to save power
● first alcohol and water can be dissolved each other with arbitrary proportion, and its dry feedstock gas can be used using this characteristic
● flow is reasonable, easy to operate
Low-temp methanol washes the removing for realizing plurality of impurities in the same apparatus, relative to a variety of net of other purification methods
For changing process combination, process is relatively single, reasonable, management easy to operation.
So in view of the raw gas complicated component and low-temp methanol washing process of crushed coal pressure gasifying can be removed disposably
The unique advantage of various impurity, the most suitable technique that undoubtedly raw gas is purified.
Methane separation as described above use cryogenic separation, and using the U.S., safe this is cold with the mixing of the neat company of Bock Lightware
Agent patented technology, -150 DEG C to -170 DEG C of temperature, preferably -155 DEG C Dao -165 DEG C, preferably pressure 3-8Mpa, 4.0-5.5Mpa, point
The compressed conduct product of methane separated out is sent outside, and the synthesis gas of separation of methane carries out higher alcohols synthesis reaction.
Higher alcohols synthesis process conditions are as described above：Reaction pressure 3.0-8.0MPa, reaction temperature 260-350
DEG C, H:Cmoleratio H2/ CO=2.0-5.0, preferably 2.3-4.2, volume space velocity 5000-50000h-1Under the conditions of carry out
The synthesis of low-carbon alcohols
Zn-Cr-K catalyst or the U.S. of the catalyst of higher alcohols synthesis as described above using Italian Snam companies
The MoS of DOW chemical companies2One kind in-M-K catalyst or the modification Cu-Zn-Al series catalysts of German Lurgi companies
The knockout tower of low-carbon alcohols separation as described above uses normal pressure or vacuum rectification tower, and operating condition is：Temperature 80-
150 DEG C, pressure is normal pressure or decompression, and the mol ratio of various alcohol is methanol 30%-65%, ethanol 5-25%, propyl alcohol 8- after separation
20%, butanol 5-20%.
The process conditions of synthesis ammonia are as described above：Reaction pressure 5-30MPa, 350-550 DEG C of reaction temperature, volume are empty
Speed is 8000-40000h-1Under the conditions of carry out ammonia synthesis reaction.
Synthetic ammonia catalyst as described above is Hubei double heroes A201Q types, A202Q types, A110Q type catalyst；Southization collects
Graduate A110-1, A110-1-h type ammonia synthesis of group is urged；One kind in the A110-2 types of Zhejiang Shangyu, A301 type catalyst.
The process conditions of urea synthesis as described above are that reaction pressure is 11-16MPa, reaction temperature 150-220
℃。
The higher alcohols synthesis and Utilization of Carbon Dioxide technique of the invention that compared with prior art, patent of the present invention provides
With advantages below：
(1) this patent takes full advantage of the synthesis gas methane content height of crushed coal pressure gasifying production, gas liquor phenol ammonia content
The characteristics of high, natural gas is made by cryogenic separation
(2) compared with existing low carbon alcohol by synthetic gas technology, this technology can produce low-carbon alcohols, utilize richness in synthesis gas
Abundant methane passes through cryogenic separation coproduction LNG, moreover it is possible to passes through the N of air separation unit2The H come is separated with low-carbon alcohols periodic off-gases2Production is closed
Ammonification, synthesis ammonia wash the CO separated with low-temp methanol again2Reaction production urea.Greenhouse gas emission is avoided, has reached CO2It is comprehensive
Utilize, realize the diversification of the product processed of synthesis gas, expanded the technology path of coal-based clean derived energy chemical.
(3) this patent is that each component is made the best use of everything in coal gas, no greenhouse gas emission, energy-conservation, water saving, investment reduction,
Technological process is simple, runs stable operation, realizes the coordinated development of economy, environment, the energy
Brief description of the drawings
The process chart of Fig. 1 present invention.
Embodiment
With reference to specific embodiment, the present invention is described in detail, it is to be understood that these embodiments are only used for more
The present invention is specifically described in detail, and the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to the limitation of following embodiments.
Embodiment 1
(1) pure synthesis gas prepares purification
Using bituminous coal as raw material, it is passed through oxygen and vapor passes through crushed coal pressure gasifying (vapor pressure 4.5MPa, gasification temperature
1200 DEG C) raw gas is made, raw gas is by the composition of percent by volume：CO：48.29 H2：24.31 CO2：14.26 CH4：
12.96 H2S：0.18；
Raw gas enters sulphur-resistant conversion of passing through under 250 DEG C, 3.5MPa, Qingdao connection letter QDB-04 type catalyst, in terms of dry gas
Calculation volume space velocity is 4000h-1, water/gas mol ratio is 0.35 after conversion；
Raw gas after conversion separates H with low-carbon alcohols periodic off-gases through PSA2Gas afterwards is washed into low-temp methanol together,
- 40 DEG C of temperature, being washed by low-temp methanol under pressure 3.5MPa makes H2S is reduced to 0.1ppm, CO2<20ppm, washed through low-temp methanol
H2S concentrated gas sends to sulfur recovery；
Raw gas after low-temp methanol is washed enters methane cryogenic separation, using the U.S. safe this and the neat company of Bock Lightware
Azeotrope, at -161 DEG C of temperature, pressure 4.4Mpa, the methane separation in raw gas is obtained into LNG (liquefied natural gas)
Product (methane volumetric fraction >=98%, sulfur content≤0.1ppm, carbon dioxide volume fraction≤1.0%), raw gas is through deep cooling
The pure synthesis gas for meeting higher alcohols synthesis is made after separation of methane
(2) higher alcohols synthesis and separation
Pure synthesis gas after cryogenic separation enters higher alcohols synthesis device, using the Zn-Cr-K of Italian Snam companies
Catalyst, in reaction pressure 4.0MPa, 300 DEG C of reaction pressure, H:Cmoleratio H2/ CO=3.0, volume space velocity 25000h-1Under the conditions of carry out low-carbon alcohols synthesis；
The periodic off-gases of synthesis of low-carbon alcohol H after PSA is separated2Synthetic ammonia tower is removed, other gas circulations are returned low-temp methanol and washed,
The mixing low-carbon alcohols synthesized through higher alcohols synthesis device enter normal pressure low-carbon alcohols rectifying separator, in tower top temperature temperature
75 DEG C, 170 DEG C of column bottom temperature, pressure is normal pressure, and reflux ratio is runoff detachment under the conditions of 2.3, separation after the mol ratio of alcohol be
Methanol 44%, ethanol 23%, propyl alcohol 18%, butanol 15%
(3) urea synthesis
The N of air separation unit2The H separated with synthesis of low-carbon alcohol periodic off-gases through PSA2Enter reactors for synthesis of ammonia together, using lake
Northern double heroes A110Q type catalyst, reaction pressure 8.0MPa, 400 DEG C of reaction temperature, volume space velocity 15000h-1Under the conditions of closed
Ammonification reacts；
The CO that the synthesis ammonia of generation is washed with low-temp methanol2Enter urea synthesis reactor together, in pressure 15MPa, temperature
Urea synthesizing is carried out under the conditions of 170 DEG C.
Embodiment 2
(1) pure synthesis gas prepares purification
Using water content be 22% lignite as raw material, be passed through oxygen and vapor pass through crushed coal pressure gasifying (vapor pressure
4.0MPa, 1240 DEG C of gasification temperature) raw gas is made, raw gas is by the composition of percent by volume：CO：49.73 H2：
25.46 CO2：10.09 CH4：14.56 H2S：0.16；
Raw gas enters under 280 DEG C, 3.8MPa, the QCS-04 series sulfur-resistant transformation catalysts of Qilu Petrochemical research institute production
Pass through sulphur-resistant conversion, volume space velocity is calculated as 3500h using dry gas-1, water/gas mol ratio is 0.28 after conversion；
Raw gas after conversion separates H with low-carbon alcohols periodic off-gases through PSA2Gas afterwards is washed into low-temp methanol together,
- 45 DEG C of temperature, being washed by low-temp methanol under pressure 4.0MPa makes H2S is reduced to 0.1ppm, CO2<20ppm, washed through low-temp methanol
H2S concentrated gas sends to sulfur recovery；
Raw gas after low-temp methanol is washed enters methane cryogenic separation, using the U.S. safe this and the neat company of Bock Lightware
Azeotrope, at -157 DEG C of temperature, pressure 5.0Mpa, the methane separation in raw gas is obtained into LNG (liquefied natural gas)
Product (methane volumetric fraction >=98%, sulfur content≤0.1ppm, carbon dioxide volume fraction≤1.0%), raw gas is through deep cooling
The pure synthesis gas for meeting higher alcohols synthesis is made after separation of methane.
(2) higher alcohols synthesis and separation
Pure synthesis gas after cryogenic separation enters higher alcohols synthesis device, using the modification Cu- of German Lurgi companies
Zn-Al series catalysts, in reaction pressure 5.0MPa, 330 DEG C of reaction pressure, H:Cmoleratio H2/ CO=3.6, volume space velocity
For 10000h-1Under the conditions of carry out low-carbon alcohols synthesis；
The periodic off-gases of synthesis of low-carbon alcohol H after PSA is separated2Synthetic ammonia tower is removed, other gas circulations are returned low-temp methanol and washed,
The mixing low-carbon alcohols synthesized through higher alcohols synthesis device enter normal pressure low-carbon alcohols rectifying separator, in tower top temperature temperature
80 DEG C, 175 DEG C of column bottom temperature, pressure is normal pressure, and reflux ratio is runoff detachment under the conditions of 2.2, separation after the mol ratio of alcohol be
Methanol 49%, ethanol 20%, propyl alcohol 17%, butanol 14%
(3) urea synthesis
The N of air separation unit2The H separated with synthesis of low-carbon alcohol periodic off-gases through PSA2Enter reactors for synthesis of ammonia together, using south
Change the graduate A110-1 of group, reaction pressure 12.0MPa, 450 DEG C of reaction temperature, volume space velocity 20000h-1Under the conditions of carry out
Ammonia synthesis reaction；
The CO that the synthesis ammonia of generation is washed with low-temp methanol2Enter urea synthesis reactor together, in pressure 13MPa, temperature
Urea synthesizing is carried out under the conditions of 200 DEG C.
Embodiment 3
(1) pure synthesis gas prepares purification
Using water content be 25% lignite as raw material, be passed through oxygen and vapor pass through crushed coal pressure gasifying (vapor pressure
5.0MPa, 1350 DEG C of gasification temperature) raw gas is made, raw gas is by the composition of percent by volume：CO：44.29 H2：
23.96 CO2：18.24 CH4：13.27 H2S：0.24；
Raw gas is carried out under 350 DEG C, 3.8MPa, the sulfur-resistant transformation catalyst of the EB series of Hubei chemical research institute exploitation
Through sulphur-resistant conversion, volume space velocity is calculated as 4500h using dry gas-1, water/gas mol ratio is 0.33 after conversion；
Raw gas after conversion separates H with low-carbon alcohols periodic off-gases through PSA2Gas afterwards is washed into low-temp methanol together,
- 45 DEG C of temperature, being washed by low-temp methanol under pressure 4.3MPa makes H2S is reduced to 0.1ppm, CO2<20ppm, washed through low-temp methanol
H2S concentrated gas sends to sulfur recovery；
Raw gas after low-temp methanol is washed enters methane cryogenic separation, using the U.S. safe this and the neat company of Bock Lightware
Azeotrope exist, -163 DEG C of temperature, under pressure 5.2Mpa, the methane separation in raw gas is obtained into LNG (liquefied natural gas)
Product (methane volumetric fraction >=98%, sulfur content≤0.1ppm, carbon dioxide volume fraction≤1.0%), raw gas is through deep cooling
The pure synthesis gas for meeting higher alcohols synthesis is made after separation of methane.
(2) higher alcohols synthesis and separation
Pure synthesis gas after cryogenic separation enters higher alcohols synthesis device, using the MoS of DOW chemical companies of the U.S.2-M-
K catalyst, in reaction pressure 6.0MPa, 320 DEG C of reaction pressure, H:Cmoleratio H2/ CO=2.6, volume space velocity are
45000h-1Under the conditions of carry out low-carbon alcohols synthesis；
The periodic off-gases of synthesis of low-carbon alcohol H after PSA is separated2Synthetic ammonia tower is removed, other gas circulations are returned low-temp methanol and washed,
The mixing low-carbon alcohols synthesized through higher alcohols synthesis device enter normal pressure low-carbon alcohols rectifying separator, in tower top temperature temperature
85 DEG C, 170 DEG C of column bottom temperature, pressure is normal pressure, and reflux ratio is runoff detachment under the conditions of 2.0, separation after the mol ratio of alcohol be
Methanol 57%, ethanol 23%, propyl alcohol 11%, butanol 9%.
(3) urea synthesis
The N of air separation unit2The H separated with synthesis of low-carbon alcohol periodic off-gases through PSA2Enter reactors for synthesis of ammonia together, using Zhejiang
Jiang Shangyu A301 type catalyst, reaction pressure 20.0MPa, 450 DEG C of reaction temperature, volume space velocity 38000h-1Under the conditions of carry out
Ammonia synthesis reaction；
The CO that the synthesis ammonia of generation is washed with low-temp methanol2Enter urea synthesis reactor together, in pressure 12MPa, temperature
Urea synthesizing is carried out under the conditions of 190 DEG C.
Embodiment 4
(1) pure synthesis gas prepares purification
Using water content be 28% lignite as raw material, be passed through oxygen and vapor by broken coal slag gasification (vapor pressure
5.0MPa, 1300 DEG C of gasification temperature) raw gas is made, raw gas is by the composition of percent by volume：CO：47.56 H2：
24.93 CO2：12.49 CH4：14.81 H2S：0.21；
Raw gas enters sulphur-resistant conversion of passing through under 350 DEG C, 4.3MPa, Qingdao connection letter QDB-04 type catalyst, in terms of dry gas
Calculation volume space velocity is 4500h-1, water/gas mol ratio is 0.36 after conversion；
Raw gas after conversion separates H with low-carbon alcohols periodic off-gases through PSA2Gas afterwards is washed into low-temp methanol together,
- 45 DEG C of temperature, being washed by low-temp methanol under pressure 5.5MPa makes H2S is reduced to 0.1ppm, CO2<20ppm, washed through low-temp methanol
H2S concentrated gas sends to sulfur recovery；
Raw gas after low-temp methanol is washed enters methane cryogenic separation, using the U.S. safe this and the neat company of Bock Lightware
Azeotrope, at -164 DEG C of temperature, pressure 4.8Mpa, the methane separation in raw gas is obtained into LNG (liquefied natural gas)
Product (methane volumetric fraction >=98%, sulfur content≤0.1ppm, carbon dioxide volume fraction≤1.0%), raw gas is through deep cooling
The pure synthesis gas for meeting higher alcohols synthesis is made after separation of methane.
(2) higher alcohols synthesis and separation
Pure synthesis gas after cryogenic separation enters higher alcohols synthesis device, using the Zn-Cr-K of Italian Snam companies
Catalyst, in reaction pressure 6.0MPa, 350 DEG C of reaction pressure, H:Cmoleratio H2/ CO=3.9, volume space velocity 40000h-1Under the conditions of carry out low-carbon alcohols synthesis；
The periodic off-gases of synthesis of low-carbon alcohol H after PSA is separated2Synthetic ammonia tower is removed, other gas circulations are returned low-temp methanol and washed,
The mixing low-carbon alcohols synthesized through higher alcohols synthesis device enter normal pressure low-carbon alcohols rectifying separator, in tower top temperature temperature
75 DEG C, 170 DEG C of column bottom temperature, pressure is normal pressure, and reflux ratio is runoff detachment under the conditions of 2.4, separation after the mol ratio of alcohol be
Methanol 60%, ethanol 15%, propyl alcohol 17%, butanol 8%.
(3) urea synthesis
The N of air separation unit2The H separated with synthesis of low-carbon alcohol periodic off-gases through PSA2Enter reactors for synthesis of ammonia together, using south
Change the graduate A110-1 types catalyst of group, reaction pressure 15.0MPa, 400 DEG C of reaction temperature, volume space velocity 30000h-1Bar
Ammonia synthesis reaction is carried out under part；
The CO that the synthesis ammonia of generation is washed with low-temp methanol2Enter urea synthesis reactor together, in pressure 14MPa, temperature
Urea synthesizing is carried out under the conditions of 210 DEG C.
Claims (10)
1. the technique of a kind of coal low-carbon alcohols and Utilization of Carbon Dioxide, it is characterised in that comprise the following steps：
(1) raw coal, from the oxygen and vapor of space division obtain raw gas through coal gas unit style, raw gas is through sulphur-resistant conversion, low temperature
Methanol is washed and the obtained pure synthesis gas for meeting higher alcohols synthesis after methane separation；Low-temp methanol washes the H isolated2S concentrated gas
Remove sulfur recovery, CO2Urea synthesizing is removed, LNG product is made in the methane that methane separation obtains；
(2) low-carbon alcohols mix products are made through higher alcohols synthesis catalyst in the synthesis gas after purifying, and low-carbon alcohols mix products are through dividing
After tower, methanol, ethanol, propyl alcohol and butanol product are isolated；
(3) higher alcohols synthesis periodic off-gases are through UF membrane, CO, CO of separation2Return to low-temp methanol to wash, the H of separation2With from space division
N2Ammonia must be synthesized into synthesis ammonia synthesis unit style；
(4) low-temp methanol washes the CO isolated2Mixed with the synthesis ammonia of step (3) and carry out urea synthesizing, obtain urea synthesis；
Described coal gas uses bituminous coal crushed coal pressurized-gasification furnace or slack coal slag gasifier, gasification temperature at 1000-1450 DEG C,
Vapor pressure is 4.0-6.0MPa；
Described conversion is using the Co-Mo sulfur-resistant transformation catalyst medium temperature sulfur resistant conversion process with high hydrolysis function, conversion pressure
Power is 2.5-4.4MPa, and transformation temperature is 220-450 DEG C, and water/gas mol ratio calculates body between 0.25-0.40, with dry gas
Product air speed is 3000-5000h-1；
The described Co-Mo sulfur-resistant transformation catalysts with high hydrolysis function are：The SSK type catalyst of Top of Denmark rope, Germany
The K8-11 type catalyst of BASF AG, the C113 type catalyst of Japanese Xing Chan Co., Ltd., the C25-2-02 of UCI companies of the U.S.
Property catalyst, Qingdao Lian Xin chemical industry Co., Ltd production QDB series sulfur-resistant transformation catalysts, Hubei chemical research institute opens
One kind in the sulfur-resistant transformation catalyst of the EB series of hair；
It is the low-temp methanol washing process for being provided with prewashing and regenerative system that described low-temp methanol, which is washed, and operation temperature is -35~-55
DEG C, operating pressure 2.0-6.0MPa, H in the synthesis gas after low-temp methanol is washed2S<0.1ppm,CO2<20ppm；
Described methane separation using the U.S. safe this and the neat company of Bock Lightware azeotrope technology, -150 DEG C of temperature to -
170 DEG C, pressure 3-8MPa.
2. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
Qingdao Lian Xin chemical industry Co., Ltd production QDB series sulfur-resistant transformation catalysts be QDB-04 type catalyst.
3. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
Higher alcohols synthesis process conditions be：Reaction pressure 3.0-8.0MPa, reaction temperature are 260-350 DEG C, H:Cmoleratio H2/
CO=2.0-5.0, volume space velocity 5000-50000h-1。
4. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 3, it is characterised in that described
H:Cmoleratio be H2/ CO=2.3-4.2.
5. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
Higher alcohols synthesis catalyst use Italian Snam companies Zn-Cr-K catalyst, the MoS of DOW chemical companies of the U.S.2-
One kind in M-K catalyst or the modification Cu-Zn-Al series catalysts of German Lurgi companies.
6. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
Low-carbon alcohols separation knockout tower use normal pressure or vacuum rectification tower, operating condition is：80-150 DEG C of temperature, pressure be normal pressure or
Decompression.
7. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
The process conditions of synthesis ammonia be：Reaction pressure 5-30MPa, 350-550 DEG C of reaction temperature, volume space velocity 8000-40000h-1。
8. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
Synthetic ammonia catalyst for Hubei double heroes A201Q types, A202Q types, A110Q type catalyst；The A110-1 of Research Institute of Nanjing Chemical Industry Group,
A110-1-h type ammonia synthesis is urged；One kind in the A110-2 types of Zhejiang Shangyu, A301 type catalyst.
9. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
The process conditions of urea synthesis be that reaction pressure is 11-16MPa, reaction temperature is 150-220 DEG C.
10. a kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide as claimed in claim 1, it is characterised in that described
Methane separation temperature be -155 DEG C to -165 DEG C, pressure 4.0-5.5MPa.
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