CN103467232A - Method for preparing alkene by using calcium carbide furnace tail gas - Google Patents
Method for preparing alkene by using calcium carbide furnace tail gas Download PDFInfo
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- CN103467232A CN103467232A CN2013103733122A CN201310373312A CN103467232A CN 103467232 A CN103467232 A CN 103467232A CN 2013103733122 A CN2013103733122 A CN 2013103733122A CN 201310373312 A CN201310373312 A CN 201310373312A CN 103467232 A CN103467232 A CN 103467232A
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- calcium carbide
- carbide stove
- stove exhaust
- alkene
- gas
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a method for preparing alkene by using calcium carbide furnace tail gas. The method mainly comprises four parts: (1), calcium carbide furnace tail gas purification part; (2), hydrogen preparation part; (3), reaction part; (4), product separation and purification part. According to the invention, the calcium carbide furnace tail gas is taken as raw material to directly prepare alkene, a novel method for comprehensively utilizing the calcium carbide furnace tail gas is provided, and a novel method for producing alkene is created; the recycle of waste resources is realized, the energy is saved, and the environmental pollution is reduced; besides, the product added value is increased by virtue of the byproduct as high-quality sweet gasoline; compared with the method of directly preparing alkene by synthetic gas, the method provided by the invention is lower in alkene production cost, and has better economic benefit.
Description
Technical field
The present invention relates to a kind of method of calcium carbide stove exhaust comprehensive utilization, particularly relate to a kind of method of utilizing calcium carbide stove exhaust to prepare alkene.
Background technology
Calcium carbide stove exhaust is the waste gas produced in calcium carbide production process.1 ton of calcium carbide of every production, produce 400～600 cubic metres of calcium carbide stove exhausts.At present, the annual calcium carbide stove exhaust produced of China surpasses 150 * 10
8m
3, disposal options is that furnace gas is in line or ignite the torch substantially, has not only wasted mass energy, also causes environmental pollution.
Due to the calcium carbide stove exhaust complicated component, the purification difficulty is large, can supply the real mature and feasible of selecting and the technology that realizes suitability for industrialized production seldom at present both at home and abroad, thereby the calcium carbide stove exhaust recovery utilization rate is always very low, and is all more low value-added utilization.For improving the utility value of calcium carbide stove exhaust, utilizing calcium carbide stove exhaust is following development trend as the Chemicals of industrial chemicals production high added value.
Change calcium carbide stove exhaust into Chemicals, develop a circular economy, improve the utilization ratio of resource, both can save coal resources, can reduce a large amount of CO again
2discharge, realize the cooperative development of economic benefit and environmental benefit.
At present, calcium carbide stove exhaust has methyl alcohol, synthetic ammonia, acetic acid, formic acid, sodium formiate, ethylene glycol etc. as the Chemicals of industrial chemicals production, but by the technology of calcium carbide stove exhaust alkene processed, report is not also arranged.
In prior art, the method that adopts non-petroleum to produce alkene mainly contains 3 kinds: (1) Sweet natural gas is alkene processed directly, namely for methane catalytically oxidative coupling legal system ethene; (2) synthetic gas alkene processed, comprise directly alkene processed, synthetic gas two kinds, alkene processed indirectly of synthetic gas, and the latter comprises that again synthesis gas through methanol Dehydration alkene and synthetic gas fermentation ethanol at first processed, ethanol are again through catalytic dehydration alkene processed; (3) bio-ethanol alkene processed, first, through fermentation ethanol processed, ethanol is again through catalytic dehydration alkene processed for biomass material.The defects such as above-mentioned these technology ubiquity production costs are relatively high, and economic benefit is low, and be subject to the restriction of current energy scarcity.
Summary of the invention
The object of the present invention is to provide a kind of waste resource that takes full advantage of, thereby realize resource reutilization, save energy, reduce production costs, and increases economic efficiency, and widens a kind of method of utilizing calcium carbide stove exhaust to prepare alkene of olefin production raw material sources.
The technical scheme taked for achieving the above object is:
A kind of method of utilizing calcium carbide stove exhaust to prepare alkene mainly comprises four parts: (1) calcium carbide stove exhaust purifies part; (2) hydrogen manufacturing part; (3) reactive moieties; (4) product separation purification part.Concrete technical scheme is as follows:
(1) by calcium carbide stove exhaust through cooling, dedusting, tar removing and desulfurization obtain sulphur content<5.0mg/m after processing
3, CO content is calcium carbide stove exhaust after 75～85% purification;
(2) wherein the rear calcium carbide stove exhaust of part purification mixes pressurization with semi-water gas, then adopts transformationreation that CO is transformed to H
2and CO
2, remove CO
2obtain H
2content reaches 90 ~ 98%, CO
2the hydrogen feed of content≤0.1 ~ 0.2%;
(3) hydrogen feed that is 90 ~ 98% by above-mentioned purity is mixed into CO/H with the rear calcium carbide stove exhaust of purification
2the mixed gas that mol ratio is 1:1 ~ 1.2, send in reactor and reacted after pressurization, heating;
(4) reacted gas-liquid mixture through cooling, gasoline splitter isolates gasoline, CO is sloughed in alkali cleaning
2after, obtain propylene and ethene by C3 knockout tower and C2 separation column successively.
Described transformationreation is middle temperature, middle temperature, low temperature, four sections series connection transformationreations of low temperature.
In described (3) process, mixed gas is forced into 2.8 ~ 3.0MPa, heats and sends in reactor after 290 ~ 310 ℃.
In described (3) process, the reaction conditions of reactor is: temperature of reaction is 260 ~ 360 ℃, and reaction pressure is controlled at 2.5 ~ 3.0MPa, and volume space velocity is 2500 ~ 2800h
-1, catalysts is the compound sections of nano level, manganese or copper-based catalysts.
Distribution 5-10 layer beds in reactor in described (3) process.
Send into gasoline splitter after 80 ~ 100 ℃ of gas-liquid mixture coolings in described (4) process.
In described (4) process, the gasoline splitter tower top temperature is 100 ~ 115 ℃, and press on top is 110 ~ 140KPa.
The compound sections of nano level of the present invention, manganese or copper-based catalysts, to ethene and propylene one way selectivity, be 60 ~ 65%, the CO transformation efficiency reaches more than 98%, this catalyzer of every 100kg can produce alkene 120kg, the high-quality sweet gasoline 25 ~ 30kg of while by-product, product propylene content 60 ~ 70%, ethylene content 20 ~ 25%.
The present invention be take calcium carbide stove exhaust and is directly prepared alkene as raw material, a kind of calcium carbide stove exhaust comprehensive utilization novel method both was provided, opened up again the novel method of olefin production, the present invention has realized the recycling of waste and old resource, has saved the energy, reduced environmental pollution, simultaneously the high-quality sweet gasoline of by-product, increased added value of product, with synthetic gas directly alkene processed compare, the olefin production cost is lower, and economic benefit is better.
The accompanying drawing explanation
Fig. 1 is calcium carbide stove exhaust purification portion division technique schema;
Fig. 2 is hydrogen manufacturing part process flow sheet;
Fig. 3 is the reactive moieties process flow sheet;
Fig. 4 is product separation purification part process flow sheet.
In figure, the meaning of each numbering representative is as follows:
| 1 | Calcium carbide stove exhaust | 2 | Coal tar | 3 | Calcium carbide stove exhaust after purifying | 4 | Semi-water gas |
| 5 | CO 2 | 6 | 90~98% | 7 | Reaction product | 8 | Gasoline |
| 9 | | 10 | | 11 | Other products such as | 12 | Ethene |
| 1-1 | Air-cooler | 1-2 | Induced draft fan | 1-3 | The dedusting water cooler | 1-4 | Roots blower |
| 1-5 | The CO gas holder | 1-6 | The static decoking device | 1-7 | Roots blower | 1-8 | Temperature-reducing tower |
| 1-9 | Thionizer | 2-1 | Compressor | 2-2 | Conversion section | 2-3 | Pressure-variable adsorption |
| 3-1 | Compressor | 3-2 | Buffer tank | 3-3 | Well heater | 3-4 | Reactor |
| 3-5 | Water cooler | 4-1 | Gasoline splitter | 4-2 | Soda-wash tower | 4-3 | The C3 separation column |
| 4-4 | The C2 knockout tower |
Embodiment
By reference to the accompanying drawings, technical scheme of the present invention is further illustrated.
(1) calcium carbide stove exhaust 1 is down to 250 ~ 260 ℃ through air-cooler 1-1 temperature, through induced draft fan 1-2, introduces dedusting water cooler 1-3, and after temperature drops to 40 ~ 50 ℃, through roots blower, 1-4 improves pressure, enters CO gas holder 1-5, and gas is further dedusting in gas holder.The calcium carbide stove exhaust of drawing from gas holder enters static decoking device 1-6, after removing the coal tar 2 of carrying secretly in tail gas, send roots blower 1-7 that gaseous tension is brought up to the 250mmHg left and right, introduce temperature-reducing tower 1-8, adopt the upper water for cooling of circulation to make gas temperature drop to 30 ~ 35 ℃, advance thionizer 1-9 desulfurization, sulfur removal technology adopts the ammoniacal liquor liquid catalytic, and its CO content reaches 75 ~ 85% left and right.Calcium carbide stove exhaust 3 sulphur contents after purifying<5.0mg/m
3, CO content 75 ~ 85% left and right.
(2) 3 parts of the calcium carbide stove exhaust after the purification are for hydrogen manufacturing.Calcium carbide stove exhaust 3 after part is purified is sent to conversion section 2-2 mixes compressed machine 2-1 pressurization with semi-water gas 4 after, in warp, in, low, hang down four sections transformationreations CO be transformed to H
2and CO
2, the CO content that goes out transformation system is controlled at≤and 0.8 ~ 1.1%.Conversion gas is removed to CO through pressure-variable adsorption 2-3
2(in Fig. 2 5), make H
2content reaches 90 ~ 98%, CO
2content≤0.1 ~ 0.2%.H as synthetic alkene
2raw material.
(3) hydrogen 6 that the purity of carrying by hydrogen generating system is 90 ~ 98% and the calcium carbide stove exhaust 3 after purification are mixed with CO/H by under meter
2the mixed gas that mol ratio is 1:1 ~ 1.2, then be transported in buffer tank 3-2 through compressor 3-1, and keeping pressure in buffer tank 3-2 is 2.8 ~ 3.0MPa.Buffer tank 3-2 outlet meets well heater 3-3, and mixed gas is heated to 290 ~ 310 ℃ of left and right, sends in reactor 3-4, and reactor 3-4 can, according to loaded catalyst, determine its diameter and height.Reactor material adopts 16MnR, in reactor, distribute 5 or 5 above beds, and catalyzer is the compound sections of nano level, manganese, copper-based catalysts, the one way selectivity that this catalyzer adds propylene to ethene is that 60 ~ 65%, CO transformation efficiency is more than 98%.The every h of every 100kg catalyzer can produce the above high-quality sweet gasoline 25 ~ 30kg of by-product simultaneously of alkene 120kg.The temperature of reaction of reactor is 260 ~ 360 ℃, and reaction pressure is controlled at 2.5 ~ 3.0MPa, and volume space velocity is 2500 ~ 2800h
-1.
(4) from reactor, gas-liquid mixture (reaction product of the label 7 shown in Fig. 3) out, by water cooler 3-5, is chilled to 80 ~ 100 ℃, then enters gasoline splitter 4-1, and its tower top temperature is 100 ~ 115 ℃, and press on top is 110 ~ 140KPa.Gasoline 8 reactor lower parts distillate by pump delivery and enter storage tank.The olefin gas mixture that top distillates, propylene content is 60 ~ 70%, and ethylene content is 20 ~ 25%, and all the other are CO
2alkane component with some C3, C4.Enter soda-wash tower 4-2 in the olefin gas mixture and remove CO
2(label shown in Fig. 49 is CO
2), isolate propylene 10 at the bottom of tower, overhead product enters C2 separation column 4-4 again, and tower top is isolated ethene 11.Propylene and ethylene product enter storage tank by refrigerant condenser respectively.
Claims (7)
1. a method of utilizing calcium carbide stove exhaust to prepare alkene is characterized in that comprising following processing step:
(1) by calcium carbide stove exhaust through cooling, dedusting, tar removing and desulfurization obtain sulphur content<5.0mg/m after processing
3, CO content is calcium carbide stove exhaust after 75～85% purification;
(2) wherein the rear calcium carbide stove exhaust of part purification mixes pressurization with semi-water gas, then adopts transformationreation that CO is transformed to H
2and CO
2, remove CO
2obtain H
2content reaches 90 ~ 98%, CO
2the hydrogen feed of content≤0.1 ~ 0.2%;
(3) hydrogen feed that is 90 ~ 98% by above-mentioned purity is mixed into CO/H with the rear calcium carbide stove exhaust of purification
2the mixed gas that mol ratio is 1:1 ~ 1.2, send in reactor and reacted after pressurization, heating;
(4) reacted gas-liquid mixture through cooling, gasoline splitter isolates gasoline, CO is sloughed in alkali cleaning
2after, obtain propylene and ethene by C3 knockout tower and C2 separation column successively.
2. according to the method for utilizing calcium carbide stove exhaust to prepare alkene claimed in claim 1, it is characterized in that described transformationreation is middle temperature, middle temperature, low temperature, four sections series connection transformationreations of low temperature.
3. according to the method for utilizing calcium carbide stove exhaust to prepare alkene claimed in claim 1, it is characterized in that in described (3) process, mixed gas is forced into 2.8 ~ 3.0MPa, heat and send in reactor after 290 ~ 310 ℃.
4. according to the method for utilizing calcium carbide stove exhaust to prepare alkene claimed in claim 1, the reaction conditions that it is characterized in that reactor in described (3) process is: temperature of reaction is 260 ~ 360 ℃, reaction pressure is controlled at 2.5 ~ 3.0MPa, and volume space velocity is 2500 ~ 2800h
-1, catalysts is the compound sections of nano level, manganese or copper-based catalysts.
5. according to the described method of utilizing calcium carbide stove exhaust to prepare alkene of claim 1 or 4, it is characterized in that in described (3) process distribution 5-10 layer beds in reactor.
6. according to the method for utilizing calcium carbide stove exhaust to prepare alkene claimed in claim 1, it is characterized in that in described (4) process sending into gasoline splitter after 80 ~ 100 ℃ of gas-liquid mixture coolings.
7. according to the method for utilizing calcium carbide stove exhaust to prepare alkene claimed in claim 1, it is characterized in that in described (4) process, the gasoline splitter tower top temperature is 100 ~ 115 ℃, press on top is 110 ~ 140KPa.
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|---|---|---|---|
| CN201310373312.2A CN103467232B (en) | 2013-08-23 | 2013-08-23 | A kind of method utilizing calcium carbide stove exhaust to prepare alkene |
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|---|---|---|---|
| CN201310373312.2A CN103467232B (en) | 2013-08-23 | 2013-08-23 | A kind of method utilizing calcium carbide stove exhaust to prepare alkene |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939840A (en) * | 2006-09-30 | 2007-04-04 | 宁夏英力特电力集团股份有限公司 | Tail gas treatment and reutilization for calcium carbide stove |
| CN101372628A (en) * | 2008-09-28 | 2009-02-25 | 陕西金巢投资有限公司 | Method for producing clean fuel oil and high-purity chemical products from calcium carbide tail gas |
| US20120029253A1 (en) * | 2008-11-19 | 2012-02-02 | Juranitch James C | Large scale green manufacturing of ethylene(ethene) using plasma |
-
2013
- 2013-08-23 CN CN201310373312.2A patent/CN103467232B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939840A (en) * | 2006-09-30 | 2007-04-04 | 宁夏英力特电力集团股份有限公司 | Tail gas treatment and reutilization for calcium carbide stove |
| CN101372628A (en) * | 2008-09-28 | 2009-02-25 | 陕西金巢投资有限公司 | Method for producing clean fuel oil and high-purity chemical products from calcium carbide tail gas |
| US20120029253A1 (en) * | 2008-11-19 | 2012-02-02 | Juranitch James C | Large scale green manufacturing of ethylene(ethene) using plasma |
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