CN204058302U - A kind of coke(oven)gas assists the system of gasification methyl alcohol - Google Patents
A kind of coke(oven)gas assists the system of gasification methyl alcohol Download PDFInfo
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- CN204058302U CN204058302U CN201420441312.1U CN201420441312U CN204058302U CN 204058302 U CN204058302 U CN 204058302U CN 201420441312 U CN201420441312 U CN 201420441312U CN 204058302 U CN204058302 U CN 204058302U
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Abstract
The utility model discloses the system that a kind of coke(oven)gas assists gasification methyl alcohol.Described system comprises the coal water slurry connected successively and prepares unit, coal gasification unit, purified synthesis gas unit and methanol synthesis unit, and coke(oven)gas purifies and separating unit, tri-reforming unit and gas mixer.The utility model is utilized by the element complementation of coal and coke(oven)gas, achieves the effective utilization to coal resources, avoids adjustment of formula and operates the effective element waste and energy penalty that cause.And carbonic acid gas and coke(oven)gas are also utilized by integrated tri-reforming unit by the utility model, make operating unit simpler, reaction process flexibility is stronger, and facility investment is also relatively little.
Description
Technical field
The utility model belongs to the energy and chemical technology field, is specifically related to the system that a kind of coke(oven)gas assists gasification methyl alcohol.
Background technology
Methyl alcohol is important Elementary Chemical Industry product, is the important source material manufacturing the multiple organic productss such as formaldehyde, acetic acid, methyl chloride, methylamine and methyl-sulfate and the C1 such as ethene and propylene chemical industry.Within 2010, China's methyl alcohol production capacity reaches 3,757 ten thousand tons, output 1,575 ten thousand tons, has become the large methanol production state of the first in the world.At present, China is mainly raw material production methyl alcohol with coal.
There is the high and CO of energy consumption in existing ammonia from coal process
2large two subject matters of quantity discharged.CO
2the major cause that quantity discharged is large and efficiency is low is that the hydrogen-carbon ratio of the crude synthesis gas that coal gasification course produces is only about 0.7, and the hydrogen-carbon ratio needed for synthesizing methanol is about 2.1, and therefore crude synthesis gas need enter water coal converter unit, and the CO in synthetic gas is converted into H
2and CO
2, so just cause a large amount of CO
2the waste of discharge and carbon, conversion process consumes a large amount of energy simultaneously.
For solving the problems referred to above existed in ammonia from coal process, the process of a kind of coal and coke(oven)gas alliance methyl alcohol (alkene) is suggested (application publication number CN 103694074 A), and this process schema as shown in Figure 1.This coal and coke(oven)gas alliance methanol process, whole by the methane in coke(oven)gas being carried out dry weight in wet base, to improve the hydrogen-carbon ratio of synthesis gas from coal gasification, avoid the synthetic gas waste that the water coal converter unit in original not methanol process processed brings, improve carbon utilization ratio and reduce CO
2discharge.But, methyl methanol syngas obtained by this technique need by four strands its formed (synthesis gas from coal gasification, dry reformed syngas, wet reformed syngas, hydrogen), turndown ratio is little, system flexibility is lower, once raw material composition changes, this technique very likely cannot obtain the synthetic gas meeting hydrogen-carbon ratio needed for methanol-fueled CLC; And the introducing of too much operating unit, also make the facility investment of this process significantly increase.
Utility model content
For solving the shortcoming and defect part of prior art, the purpose of this utility model is to provide a kind of coke(oven)gas to assist the system of gasification methyl alcohol.
For realizing above-mentioned utility model object, the utility model adopts following technical scheme:
A kind of coke(oven)gas assists the system of gasification methyl alcohol, comprise coal water slurry and prepare unit, coal gasification unit, purified synthesis gas unit, coke(oven)gas purification and separating unit, gas mixer and methanol synthesis unit, described coal water slurry is prepared unit and is provided with raw coal entrance, the coal water slurry outlet that coal water slurry prepares unit is connected with the coal water slurry entrance of coal gasification unit by pipeline, the gasification crude synthesis gas outlet of coal gasification unit is connected with the gasification crude synthesis gas entrance of purified synthesis gas unit by pipeline, gasification crude synthesis gas outlet after the purification of purified synthesis gas unit is connected with gas mixer by pipeline, coke(oven)gas purification is provided with thick coke(oven)gas entrance with separating unit, and coke(oven)gas purification is connected with gas mixer by pipeline with the hydrogen outlet of separating unit, the methyl alcohol reacting synthesis gas outlet of gas mixer is connected with the methyl methanol syngas entrance of methanol synthesis unit by pipeline, described system also comprises tri-reforming unit,
The carbon dioxide outlet of described purified synthesis gas unit is connected with the carbonic acid gas entrance of tri-reforming unit by pipeline;
Described coke(oven)gas purification is exported with the methane gas of separating unit and is connected with the methane gas entrance of tri-reforming unit by pipeline; The tri-reforming syngas outlet of described tri-reforming unit is connected with gas mixer by pipeline, and tri-reforming unit is also provided with oxygen intake and steam entry.
Adopt said system to prepare the technique of methyl alcohol, processing step is as follows:
Feed coal is prepared after unit makes coal water slurry in coal water slurry, enters coal gasification unit and carries out coal gasification reaction, obtained gasification crude synthesis gas together with oxygen; Gasification crude synthesis gas enters purified synthesis gas unit and removes sulfide and carbonic acid gas, the gasification crude synthesis gas after being purified and carbonic acid gas;
The thick coke(oven)gas of raw material enters coke(oven)gas purification and separating unit, obtains methane gas, hydrogen and impurity through purification after being separated; Carbonic acid gas, oxygen and water vapour that described methane gas, purified synthesis gas unit obtain enter tri-reforming unit jointly, obtained tri-reforming synthetic gas; Gasification crude synthesis gas after the purification that described tri-reforming synthetic gas, purified synthesis gas unit obtain and coke(oven)gas purify the hydrogen obtained with separating unit and jointly enter gas mixer, after mixing, obtain methyl alcohol reacting synthesis gas; Described methyl alcohol reacting synthesis gas enters methanol synthesis unit, obtains methanol product through reaction with after purifying.
Preferably, the charge-mass ratio of the thick coke(oven)gas of described raw material and feed coal is (3 ~ 8): 1, and wherein the quality of thick coke(oven)gas amounts to into the Mass Calculation of standard coal by calorific value.
Preferably, the hydrogen-carbon ratio of described gasification crude synthesis gas is 0.5 ~ 1.0.
Preferably, the composition of the thick coke(oven)gas of described raw material comprises the H that volume fraction is 55 ~ 60%
2be the CH of 20 ~ 27% with volume fraction
4, the hydrogen-carbon ratio of the thick coke(oven)gas of raw material after purifying through purification and separating unit is 5 ~ 7.
Preferably, the service temperature of described tri-reforming unit is 800 ~ 900 DEG C, and working pressure is 1atm.
Preferably, the sepn process of described thick coke(oven)gas is pressure-swing adsorption process.
Principle of the present utility model is: make full use of coke(oven)gas, not only will consider its high hydrogen-carbon ratio, but also will consider the CH with high utility value
4, produce CO and H by reforming
2.Methane reforming have 3 by way of, namely for methane steam reforming, methane carbon dioxide reformation, and methane portion oxidation.Wherein, methane vapor reforming methane reforming with carbon dioxide is all thermo-negative reaction, process energy consumption is high, and methane carbon dioxide reformation is thermopositive reaction, if methane vapor reforming, methane carbon dioxide reformation, methane portion oxidation are coupled (methane tri-reforming), then the energy of thermopositive reaction can be used for thermo-negative reaction, and realization response is from heat supply.Therefore, the utility model utilizes this tri-reforming coupling coke(oven)gas and gasification gas to carry out methanol production.
As compared to the technology of existing coal with coke(oven)gas alliance methyl alcohol, the utility model has the following advantages and beneficial effect:
(1) current coal and coke(oven)gas alliance methanol process is compared, the utility model does reforming reaction, methane-steam reforming and partial oxidation reaction of methane by the methane tri-reforming device methane that has been coupled, this makes production process by a tri-reforming unit, instead of the whole reaction member of original methane dry weight and methane-steam reforming unit, simplify the operating unit of coal and preparing methanol from coke oven gas process, reduce facility investment.
(2) methyl methanol syngas of current coal and coke(oven)gas alliance methanol process, combined by three bursts of logistics, therefore the turndown ratio of system is lower at present, when raw material composition slightly changes, just cannot obtain the synthetic gas meeting methanol-fueled CLC demand, system flexibility is low.The new process that the utility model proposes decreases the composition stream sizes of methyl methanol syngas, improves system flexibility and turndown ratio.Meanwhile, owing to simplifying technique, operational stability is high.
(3) compare current coal and coke(oven)gas alliance methanol process, the utility model is owing to decreasing the whole and steam reforming unit of the higher methane dry weight of energy consumption, and therefore the efficiency of process can improve more than 8%, and carbon utilization ratio can improve more than 5%.
Accompanying drawing explanation
Fig. 1 is current coal and coke(oven)gas alliance methanol technics schematic diagram.Wherein 101 prepare unit for coal water slurry, and 102 is coal gasification unit, and 103 is purified synthesis gas unit, 104 is methanol synthesis unit, and 105 is coke(oven)gas purification and separating unit, and 106 is the dry reformer unit of methane, 107 is methane vapor reforming unit, and 108 is gas mixer; 200 ~ 215 is logistics numbering, and wherein 200 is feed coal, and 201 is coal water slurry, 202 is oxygen, and 203 is gasification crude synthesis gas, and 204 is the gasification crude synthesis gas after purification, 205,215 is carbonic acid gas, 206 is methyl methanol syngas, and 207 is methyl alcohol, and 208 is coke(oven)gas, 209,210,211 is methane, 212 is hydrogen, and 213 is dry reformed syngas, 214 wet reformed syngas.
Fig. 2 is that coke(oven)gas of the present utility model assists ammonia from coal system process schematic diagram.Wherein 109 is tri-reforming unit; 200 ~ 218 is logistics numbering, and wherein 216 is oxygen, and 217 is water vapour, and 218 is tri-reforming synthetic gas, and 219 is that the coke(oven)gas such as tar purify the impurity obtained, all the other the numbering operating unit identical with same reference numeral in Fig. 1 or logistics.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the utility model is described in further detail, but embodiment of the present utility model is not limited thereto.
A kind of coke(oven)gas of the utility model assists the system of gasification methyl alcohol, as shown in Figure 2, comprise coal water slurry and prepare unit 101, coal gasification unit 102, purified synthesis gas unit 103, coke(oven)gas purification and separating unit 105, gas mixer 108 and methanol synthesis unit 104, described coal water slurry is prepared unit 101 and is provided with raw coal entrance, the coal water slurry outlet that coal water slurry prepares unit 101 is connected with the coal water slurry entrance of coal gasification unit 102 by pipeline, the gasification crude synthesis gas outlet of coal gasification unit 102 is directly connected with the gasification crude synthesis gas entrance of purified synthesis gas unit 103 by pipeline, gasification crude synthesis gas outlet after the purification of purified synthesis gas unit 103 is connected with gas mixer 108 by pipeline, coke(oven)gas purification is provided with thick coke(oven)gas entrance with separating unit 105, and coke(oven)gas purification is connected with gas mixer 108 by pipeline with the hydrogen outlet of separating unit 105, the methyl alcohol reacting synthesis gas outlet of gas mixer 108 is connected with the methyl methanol syngas entrance of methanol synthesis unit 104 by pipeline, described system also comprises tri-reforming unit 109,
The carbon dioxide outlet of purified synthesis gas unit 103 is connected with the carbonic acid gas entrance of tri-reforming unit 109 by pipeline; Coke(oven)gas purification is exported with the methane gas of separating unit 105 and is connected with the methane gas entrance of tri-reforming unit 109 by pipeline; The tri-reforming syngas outlet of tri-reforming unit 109 is connected with gas mixer 108 by pipeline.
Coal gasification unit 102 is also provided with oxygen intake, and coke(oven)gas purification is also provided with coke(oven)gas with separating unit 105 and purifies impurities outlet, and methanol synthesis unit 104 is also provided with methanol outlet; Tri-reforming unit 109 is also provided with oxygen intake and steam entry.
Can see from Fig. 2, the processing step that the utility model employing said system prepares methyl alcohol is as follows:
Feed coal 200 is prepared after unit 101 makes coal water slurry 201 through coal water slurry, enters coal gasification unit 102 and carries out coal gasification reaction, obtained gasification crude synthesis gas 203 together with oxygen 202; Gasification crude synthesis gas 203 enters purified synthesis gas unit 103 and removes sulfide and carbonic acid gas, the synthesis gas from coal gasification 204 after being purified and carbonic acid gas 205;
The thick coke(oven)gas 208 of raw material enters coke(oven)gas purification and separating unit 105, obtains methane gas 209, hydrogen 212 and impurity 219 through purification after being separated; Carbonic acid gas 205, oxygen 216 and water vapour 217 that described methane gas 209 and purified synthesis gas unit 103 obtain enter tri-reforming unit 109 jointly, obtained tri-reforming synthetic gas 218; Synthesis gas from coal gasification 204 after the purification that described tri-reforming synthetic gas 218, purified synthesis gas unit 103 obtain and coke(oven)gas purify the hydrogen 212 obtained with separating unit 105 and jointly enter gas mixture 108, after mixing, obtain methyl alcohol reacting synthesis gas 206; Described methyl alcohol reacting synthesis gas 206 enters methanol synthesis unit 104, obtains methanol product 207 through reaction with after purifying.
Coke(oven)gas of the present utility model assists the difference of the prior art shown in gasification methyl alcohol system and Fig. 1 to be:
(1) in system of the present utility model, by the methane purifying rear coke(oven)gas resulting separation, do not need to enter respectively the whole and wet reformer unit of dry weight to produce synthetic gas, but directly enter tri-reforming unit.Tri-reforming can absorb the CO of coal gasification course discharge
2.Coke(oven)gas is separated the hydrogen obtained and then with directly mixes with the synthetic gas after gasification and tri-reforming, to regulate hydrogen-carbon ratio.
(2), in system of the present utility model, the synthetic gas needed for methanol-fueled CLC is by synthesis gas from coal gasification, tri-reforming synthetic gas and be separated by coke(oven)gas the hydrogen obtained and form, and the hydrogen-carbon ratio of this synthetic gas is about 2.1 ~ 2.15.Compare coal methanol process processed separately, the synthetic gas that the flow process that the utility model proposes produces regulates hydrogen-carbon ratio without the need to entering water coal converter unit.
Embodiment 1
The coke(oven)gas of the present embodiment assists specifically being implemented as follows of gasification methyl alcohol system:
The feed coal flow entering the utility model system process is 250t/h.Raw coke oven gas flow is 350t/h.The composition of coke(oven)gas is in table 1.Coke(oven)gas assists the total figure of ammonia from coal technical process see Fig. 2:
Feed coal 200 is prepared after unit makes coal water slurry 201 through coal water slurry, enters coal gasification unit 101 and carries out coal gasification reaction, obtained gasification crude synthesis gas 203 together with oxygen 202; Gasification crude synthesis gas 203 enters purified synthesis gas unit 103 and removes sulfide and carbonic acid gas, the synthesis gas from coal gasification 204 after being purified and carbonic acid gas 205;
The thick coke(oven)gas 208 of raw material enters coke(oven)gas purification and separating unit 105, obtains methane gas 209, hydrogen 212 and impurity 219 through purification after being separated; Carbonic acid gas 205, oxygen 216 and water vapour 217 that described methane gas 209 and purified synthesis gas unit 103 obtain enter tri-reforming unit 109 jointly, obtained tri-reforming synthetic gas 218; Synthesis gas from coal gasification 204 after the purification that described tri-reforming synthetic gas 218, purified synthesis gas unit 103 obtain and coke(oven)gas purify the hydrogen 212 obtained with separating unit 105 and jointly enter gas mixture 108, after mixing, obtain methyl alcohol reacting synthesis gas 206; Described methyl alcohol reacting synthesis gas 206 enters methanol synthesis unit 104, obtains methanol product 207 through reaction with after purifying.
Wherein, the service temperature of tri-reforming device is 850 DEG C, and working pressure is 1atm, and other operating units are with reference to current ammonia from coal process operating mode.
The composition of table 1 coke(oven)gas
| Composition | H 2 | CH 4 | CO | CO 2 | N 2 | O 2 | C mH n |
| Volume fraction % | 59.5 | 24.8 | 6.5 | 5.5 | 3.2 | 0.3 | 0.2 |
Carry out modeling Simulation by process simulation software Aspen to the present embodiment meter, its analog result is in table 2.
Table 2 analog result
| Logistics is numbered | 203 | 211 | 213 | 214 | 209 | 215 | 212 | 217 |
| Molar fraction | ? | ? | ? | ? | ? | ? | ? | ? |
| N 2 | 0.004 | 0.006 | 0.01 | 0 | 0.006 | 0.005 | 0.067 | 0.019 |
| O 2 | trace | 0.002 | 0.95 | 0 | trace | trace | 0.006 | 0.002 |
| Ar | 0.001 | 0 | 0.04 | 0 | 0.001 | trace | 0 | Trace |
| H 2O | 0.224 | trace | 0 | 1.0 | trace | trace | 0 | trace |
| CO | 0.356 | 0.014 | 0 | 0 | 0.558 | 0.330 | 0.086 | 0.319 |
| COS | trace | 0 | 0 | 0 | trace | trace | 0 | trace |
| CO 2 | 0.135 | trace | 0 | 0 | trace | 0.005 | 0 | 0.003 |
| H 2S | 0.003 | trace | 0 | 0 | trace | trace | trace | trace |
| H 2 | 0.277 | 0.002 | 0 | 0 | 0.434 | 0.660 | 0.84 | 0.652 |
| CH 4 | trace | 0.976 | 0 | 0 | trace | trace | 0.001 | 0.005 |
| Molar flow, kmol/hr | 28202 | 7495 | 678 | 4212 | 17993 | 27105 | 19645 | 64743 |
| Mass rate, t/hr | 598.3 | 122 | 21.9 | 75.8 | 301 | 295 | 121.2 | 717.3 |
| Temperature, DEG C | 152 | 65 | 110 | 25 | 240 | 240 | 240 | 240 |
| Pressure, bar | 28 | 23 | 41 | 1.0 | 23 | 82 | 82 | 82 |
The unit consumption of product of technical process and energy expenditure, calculate energy efficiency through signature.Can see from table 2, tri-reforming unit absorbs the CO of 56% of gasification generation
2, and CH
4be converted into CO and H together
2, not only reduce CO
2discharge, and add the amount of available gas, synthesize more methyl alcohol.Now, CO
2reduce discharging 61.2%, carbon utilization ratio brings up to 84.1%.Due to the raising of carbon utilization ratio, the raw coal consumption making alliance process produce identical amount methanol product is only 28% of independent ammonia from coal process, the total energy significantly reducing system drops into, therefore this process has higher efficiency, improves 16.8 percentage points than independent ammonia from coal process.
By above-mentioned the present embodiment 1 and coal of the prior art and coke(oven)gas alliance methyl alcohol (concrete technology as shown in Figure 1) and coal separately methanol technics processed compare, result is as shown in table 3.Compare coal and coke(oven)gas alliance methanol technics, efficiency of the present utility model improves 13%, and carbon utilization ratio improves 6%.Compare coal methanol technics processed separately, efficiency of the present utility model improves 17%, carbon utilization ratio improve 28%.
Table 3 the utility model and ammonia from coal leading indicator contrast
Above-described embodiment is the utility model preferably embodiment; but embodiment of the present utility model is not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present utility model and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection domain of the present utility model.
Claims (1)
1. a coke(oven)gas assists the system of gasification methyl alcohol, comprise coal water slurry and prepare unit, coal gasification unit, purified synthesis gas unit, coke(oven)gas purification and separating unit, gas mixer and methanol synthesis unit, described coal water slurry is prepared unit and is provided with raw coal entrance, the coal water slurry outlet that coal water slurry prepares unit is connected with the coal water slurry entrance of coal gasification unit by pipeline, the gasification crude synthesis gas outlet of coal gasification unit is connected with the gasification crude synthesis gas entrance of purified synthesis gas unit by pipeline, gasification crude synthesis gas outlet after the purification of purified synthesis gas unit is connected with gas mixer by pipeline, coke(oven)gas purification is provided with thick coke(oven)gas entrance with separating unit, and coke(oven)gas purification is connected with gas mixer by pipeline with the hydrogen outlet of separating unit, the methyl alcohol reacting synthesis gas outlet of gas mixer is connected with the methyl methanol syngas entrance of methanol synthesis unit by pipeline, it is characterized in that, described system also comprises tri-reforming unit,
The carbon dioxide outlet of described purified synthesis gas unit is connected with the carbonic acid gas entrance of tri-reforming unit by pipeline;
Described coke(oven)gas purification is exported with the methane gas of separating unit and is connected with the methane gas entrance of tri-reforming unit by pipeline; The tri-reforming syngas outlet of described tri-reforming unit is connected with gas mixer by pipeline, and tri-reforming unit is also provided with oxygen intake and steam entry.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193585A (en) * | 2014-08-06 | 2014-12-10 | 华南理工大学 | System and process for preparing methyl alcohol through coke-oven gas-assisted coal gasification |
| CN109020780A (en) * | 2018-08-03 | 2018-12-18 | 华南理工大学 | A kind of coal gasification coupling coking of coal methanol system and method |
-
2014
- 2014-08-06 CN CN201420441312.1U patent/CN204058302U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193585A (en) * | 2014-08-06 | 2014-12-10 | 华南理工大学 | System and process for preparing methyl alcohol through coke-oven gas-assisted coal gasification |
| CN109020780A (en) * | 2018-08-03 | 2018-12-18 | 华南理工大学 | A kind of coal gasification coupling coking of coal methanol system and method |
| CN109020780B (en) * | 2018-08-03 | 2021-08-10 | 华南理工大学 | System and method for preparing methanol by coal gasification coupled coal coking |
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