CN103467232B - A kind of method utilizing calcium carbide stove exhaust to prepare alkene - Google Patents
A kind of method utilizing calcium carbide stove exhaust to prepare alkene Download PDFInfo
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- CN103467232B CN103467232B CN201310373312.2A CN201310373312A CN103467232B CN 103467232 B CN103467232 B CN 103467232B CN 201310373312 A CN201310373312 A CN 201310373312A CN 103467232 B CN103467232 B CN 103467232B
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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 present invention relates to a kind of method utilizing calcium carbide stove exhaust to prepare alkene, the method mainly comprises four parts: (1) calcium carbide stove exhaust purification part; (2) hydrogen manufacturing part; (3) reactive moieties; (4) product separation purification part.The present invention is that raw material directly prepares alkene with calcium carbide stove exhaust, both a kind of calcium carbide stove exhaust comprehensive utilization novel method had been provided, open again the novel method of olefin production, present invention achieves the recycling of waste and old resource, save the energy, decrease environmental pollution, by-product high-quality sweet gasoline, adds added value of product, compared with synthetic gas directly alkene processed simultaneously, olefin production cost is lower, and economic benefit is better.
Description
Technical field
The present invention relates to the method for a kind of calcium carbide stove exhaust comprehensive utilization, particularly relate to a kind of method utilizing calcium carbide stove exhaust to prepare alkene.
Background technology
Calcium carbide stove exhaust is the waste gas produced in calcium carbide production process.Often produce 1 ton of calcium carbide, produce 400 ~ 600 cubic metres of calcium carbide stove exhausts.At present, the calcium carbide stove exhaust that produces every year of China is more than 150 × 10
8m
3, disposal options is that furnace gas is in line or ignite the torch substantially, not only wastes mass energy, also causes environmental pollution.
Due to calcium carbide stove exhaust complicated component, purification difficulty is large, both at home and abroad at present can for the real mature and feasible selected and to realize the technology of suitability for industrialized production little, and thus, 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, calcium carbide stove exhaust is utilized to be 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, and a large amount of CO can be reduced again
2discharge, realizes 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 that industrial chemicals is produced, but does not also have report by the technology of calcium carbide stove exhaust alkene.
In prior art, the method adopting non-petroleum feedstocks to produce alkene mainly contains 3 kinds: (1) Sweet natural gas directly alkene processed, namely for methane catalytically oxidative coupling legal system ethene; (2) synthetic gas alkene, comprises synthetic gas directly alkene processed, synthetic gas two kinds, alkene processed indirectly, and the latter comprises again synthesis gas through methanol Dehydration alkene and synthetic gas ferments ethanol first processed, ethanol again through catalytic dehydration alkene; (3) bio-ethanol alkene, namely biomass material is first through fermentation ethanol, and ethanol is again through catalytic dehydration alkene.These technology ubiquity production costs above-mentioned are relatively high, the defects such as economic benefit is low, and are subject to current energy source restriction in short supply.
Summary of the invention
The object of the present invention is to provide one to make full use of waste resource, thus realize resource reutilization, save energy, reduce production cost, increase economic efficiency, widen a kind of method utilizing calcium carbide stove exhaust to prepare alkene of olefin production raw material sources.
Technical scheme taked for achieving the above object is:
Utilize calcium carbide stove exhaust to prepare a method for alkene, mainly comprise four parts: (1) calcium carbide stove exhaust purification 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, obtains sulphur content < 5.0mg/m after tar removing and desulfurization process
3, CO content is calcium carbide stove exhaust after the purification of 75 ~ 85%;
(2) will wherein after a part purification calcium carbide stove exhaust mix with semi-water gas and pressurize, then CO is transformed to H by employing transformationreation
2and CO
2, remove CO
2obtain H
2content reaches 90 ~ 98%, CO
2the hydrogen feed of content≤0.1 ~ 0.2%;
(3) by above-mentioned purity be 90 ~ 98% hydrogen feed with purification after calcium carbide stove exhaust be mixed into CO/H
2mol ratio is the mixed gas of 1:1 ~ 1.2, sends in reactor and react after pressurization, heating;
(4) reacted gas-liquid mixture through cooling, gasoline isolated by gasoline splitter, 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, low temperature four sections series connection transformationreation.
In described (3) process, mixed gas is forced into 2.8 ~ 3.0MPa, heats to send in reactor after 290 ~ 310 DEG C.
In described (3) process, the reaction conditions of reactor is: temperature of reaction is 260 ~ 360 DEG C, and reaction pressure controls at 2.5 ~ 3.0MPa, and volume space velocity is 2500 ~ 2800h
-1, catalysts is nano level compound sections, manganese or copper-based catalysts.
Distribute in reactor in described (3) process 5-10 layer beds.
Gasoline splitter is sent into after gas-liquid mixture cooling 80 ~ 100 DEG C in described (4) process.
In described (4) process, gasoline splitter tower top temperature is 100 ~ 115 DEG C, and top pressure is 110 ~ 140KPa.
Nano level compound sections of the present invention, manganese or copper-based catalysts, be 60 ~ 65% to ethene and propylene one way selectivity, CO transformation efficiency reaches more than 98%, this catalyzer of every 100kg can produce alkene 120kg, by-product high-quality sweet gasoline 25 ~ 30kg simultaneously, product propylene content 60 ~ 70%, ethylene content 20 ~ 25%.
The present invention is that raw material directly prepares alkene with calcium carbide stove exhaust, both a kind of calcium carbide stove exhaust comprehensive utilization novel method had been provided, open again the novel method of olefin production, present invention achieves the recycling of waste and old resource, save the energy, decrease environmental pollution, by-product high-quality sweet gasoline, adds added value of product, compared with synthetic gas directly alkene processed simultaneously, olefin production cost is lower, and economic benefit is better.
Accompanying drawing explanation
Fig. 1 is calcium carbide stove exhaust purification portion division technique schema;
Fig. 2 is hydrogen manufacturing some processes schema;
Fig. 3 is reactive moieties process flow sheet;
Fig. 4 is product separation purification some processes schema.
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 purification | 4 | Semi-water gas |
| 5 | CO 2 | 6 | 90~98%H 2 | 7 | Reaction product | 8 | Gasoline |
| 9 | CO 2 | 10 | Propylene | 11 | Other products such as ethane | 12 | Ethene |
| 1-1 | Air-cooler | 1-2 | Induced draft fan | 1-3 | Dedusting water cooler | 1-4 | Roots blower |
| 1-5 | CO gas holder | 1-6 | Electrostatic 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 | C3 separation column |
| 4-4 | 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 DEG C through air-cooler 1-1 temperature, and introduce dedusting water cooler 1-3 through induced draft fan 1-2, after temperature drops to 40 ~ 50 DEG C, improved by pressure through roots blower 1-4, enter CO gas holder 1-5, gas is further dedusting in gas holder.The calcium carbide stove exhaust of drawing from gas holder enters electrostatic decoking device 1-6, after the coal tar 2 carried secretly in removing tail gas, send roots blower 1-7 that gaseous tension is brought up to about 250mmHg, introduce temperature-reducing tower 1-8, the upper water for cooling of circulation is adopted to make gas temperature drop to 30 ~ 35 DEG C, enter thionizer 1-9 desulfurization, sulfur removal technology adopts ammoniacal liquor liquid catalytic, and its CO content reaches about 75 ~ 85%.Calcium carbide stove exhaust 3 sulphur content < 5.0mg/m after purification
3, CO content about 75 ~ 85%.
(2) calcium carbide stove exhaust 3 part after purification is used for hydrogen manufacturing.Calcium carbide stove exhaust 3 after Partial cleansing is mixed with semi-water gas 4 after compressor 2-1 pressurizes, is sent to conversion section 2-2, through in, in, low, low four sections of transformationreations are transformed to H CO
2and CO
2, the CO content going out transformation system controls≤0.8 ~ 1.1%.Conversion gas is removed CO through pressure-variable adsorption 2-3
2(in Fig. 2 5), make H
2content reaches 90 ~ 98%, CO
2content≤0.1 ~ 0.2%.As the H of synthesis alkene
2raw material.
(3) purity of coming is carried to be that the hydrogen 6 of 90 ~ 98% and the calcium carbide stove exhaust 3 after purifying are mixed with CO/H by under meter by hydrogen generating system
2mol ratio is the mixed gas of 1:1 ~ 1.2, is then transported in buffer tank 3-2 through compressor 3-1, keeps pressure to be 2.8 ~ 3.0MPa in buffer tank 3-2.Buffer tank 3-2 outlet meets well heater 3-3, mixed gas is heated to about 290 ~ 310 DEG C, sends in reactor 3-4, and reactor 3-4 according to loaded catalyst, can determine its diameter and height.Reactor material adopts 16MnR, distribution more than 5 or 5 beds in reactor, and catalyzer is nano level compound sections, manganese, copper-based catalysts, and the one way selectivity that this catalysts towards ethylene adds propylene is 60 ~ 65%, CO transformation efficiency is more than 98%.The every h of every 100kg catalyzer can produce more than alkene 120kg by-product high-quality sweet gasoline 25 ~ 30kg simultaneously.The temperature of reaction of reactor is 260 ~ 360 DEG C, and reaction pressure controls at 2.5 ~ 3.0MPa, and volume space velocity is 2500 ~ 2800h
-1.
(4) by water cooler 3-5, be chilled to 80 ~ 100 DEG C from reactor gas-liquid mixture (reaction product of the label 7 shown in Fig. 3) out, then enter gasoline splitter 4-1, its tower top temperature is 100 ~ 115 DEG C, and top pressure is 110 ~ 140KPa.Gasoline 8 reactor lower part distillates and enters storage tank by pump delivery.The olefin gas mixture that top distillates, propylene content is 60 ~ 70%, and ethylene content is 20 ~ 25%, and all the other are CO
2with the alkane component of some C3, C4.Enter soda-wash tower 4-2 in olefin gas mixture and remove CO
2(label 9 shown in Fig. 4 is CO
2), isolate propylene 10 at the bottom of tower, overhead product enters C2 separation column 4-4 again, and tower top isolates ethene 11.Propylene and ethylene product enter storage tank respectively by refrigerant condenser.
Claims (4)
1. utilize calcium carbide stove exhaust to prepare a method for alkene, it is characterized in that comprising following processing step:
(1) by calcium carbide stove exhaust through cooling, dedusting, obtains sulphur content < 5.0mg/m after tar removing and desulfurization process
3, CO content is calcium carbide stove exhaust after the purification of 75 ~ 85%;
(2) will wherein after a part purification calcium carbide stove exhaust mix with semi-water gas and pressurizes, then CO is transformed to H by the transformationreation of connecting of temperature in employing, middle temperature, low temperature, low temperature four sections
2and CO
2, remove CO
2obtain H
2content reaches 90 ~ 98%, CO
2the hydrogen feed of content≤0.1 ~ 0.2%;
(3) by above-mentioned purity be 90 ~ 98% hydrogen feed with purification after calcium carbide stove exhaust be mixed into CO/H
2mol ratio is the mixed gas of 1:1 ~ 1.2, and be forced into 2.8 ~ 3.0Mpa, heat to send in reactor after 290 ~ 310 DEG C and react, reaction conditions is: temperature of reaction is 260 ~ 360 DEG C, and reaction pressure controls at 2.5 ~ 3.0MPa, and volume space velocity is 2500 ~ 2800h
-1, catalysts is nano level compound sections, manganese or copper-based catalysts;
(4) reacted gas-liquid mixture through cooling, gasoline isolated by gasoline splitter, 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 utilizing calcium carbide stove exhaust to prepare alkene according to claim 1, it is characterized in that distributing in reactor in described (3) process 5-10 layer beds.
3., according to the method utilizing calcium carbide stove exhaust to prepare alkene according to claim 1, it is characterized in that sending into gasoline splitter after gas-liquid mixture cooling 80 ~ 100 DEG C in described (4) process.
4., according to the method utilizing calcium carbide stove exhaust to prepare alkene according to claim 1, it is characterized in that in described (4) process, gasoline splitter tower top temperature is 100 ~ 115 DEG C, top pressure is 110 ~ 140KPa.
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|---|---|---|---|
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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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| CN103467232B true CN103467232B (en) | 2015-09-02 |
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Citations (2)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010059223A1 (en) * | 2008-11-19 | 2010-05-27 | Global Energies, Llc | Large scale green manufacturing of ethylene (ethene) using plasma |
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2013
- 2013-08-23 CN CN201310373312.2A patent/CN103467232B/en active Active
Patent Citations (2)
| 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 |
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