CN100336715C - Process for preparing hydrogen by part changing of yellow phosphorus tail gas - Google Patents
Process for preparing hydrogen by part changing of yellow phosphorus tail gas Download PDFInfo
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- CN100336715C CN100336715C CNB2005100108407A CN200510010840A CN100336715C CN 100336715 C CN100336715 C CN 100336715C CN B2005100108407 A CNB2005100108407 A CN B2005100108407A CN 200510010840 A CN200510010840 A CN 200510010840A CN 100336715 C CN100336715 C CN 100336715C
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Abstract
The present invention relates to a method for preparing hydrogen by part conversion of yellow phosphorus tail gas. Purified yellow phosphorus tail gas is proportionally mixed with water vapor; one part of the mixed gas is introduced into a heat exchanger and is introduced into a conversion reactor filled with catalyzer after being heated; the other part of the mixed gas is used as quenching gas to be directly introduced into the conversion reactor for conversion reaction; an indirect heat exchanger is adopted between the second segment and the third segment of a converter; the heat quantity of conversion gas in the second segment is transferred to the purified gas of the yellow phosphorus tail gas coming from a purification system; after temperature drop, the conversion gas in the second segment enters a third segment reaction vessel to continuously carry out conversion reaction; finally, mixed conversion gas of hydrogen, carbon monoxide and carbon dioxide are prepared. The catalyzer does not use condensed water; the present invention has the advantages of little steam dosage, no phenomenon of casing accumulation generation, little inorganic salt, low resistance of catalyst layer, and long service life of catalysts. The prepared mixed gas of hydrogen, carbon monoxide and carbon dioxide can meet the purpose of preparing chemical and industrial carbon products.
Description
(1), technical field: the invention belongs to gas reforming chemical industry preparation field,
(2), background technology: 1 ton of yellow phosphorus of general every production, discharge 2500-3000Nm
3Yellow phosphoric tail gas contains CO 85-92%, CO in the tail gas
22-4%, 500-800mg phosphorus/Nm
3, 1-2mg arsenic/Nm
3,-500mg fluorine/Nm
3,-300mg sulphur/Nm
3And moisture content.Because sulphur, phosphorus, arsenic, fluorine etc. all are that the burn into objectionable impurities is arranged.Influenced the utilization of yellow phosphoric tail gas.At present, the phosphorus production producer in the whole nation has only minority to utilize part tail gas in the oven dry of raw material or make the fuel gas of dry tripoly phosphate sodium STPP, and indivedual producers utilize yellow phosphoric tail gas to produce phosgene and sodium formiate, methyl-formiate, formic acid, methylcarbonate etc.Most of producers all end utilize, and in a mode of sky lamp, and burning with chimney stack (being generally the 30m height) enters atmosphere, both severe contamination atmospheric environment, be again the significant wastage of carbon monoxide resource.
Since the eighties, a carbonizer relevant technologies is competitively developed in countries in the world, and this field development is rapid, and also there is large development in China.One carbonizer is by coal, Sweet natural gas set out preparing synthetic gas (CO, H
2) or be raw material by the carbon monoxide of industrial production by-product etc., many carbonizer's products production producers adopt the water-gas method for obtaining the carbon monoxide source of the gas, carry dense CO through purification, as raw material.Under different catalyzer and processing condition, carry out carbonylation reaction (as oxo process, rowland reaction, reppe reactions, fischer-tropsch synthetic etc.), synthol, acid, ester and synthetic all kinds of important fuel of wet goods and organic chemical industry's product.Make the utilization of carbon monoxide become possibility, utilize the yellow phosphoric tail gas that contains carbon monoxide nearly 90%, by purifying the synthetic carbonizer's product in back, both avoided environmental pollution, can reduce the production cost of yellow phosphorus again, it is too high because of cost to change present phosphorus production, nocompetitive situation on market.
At present, be used for the coal gas of carbon monodixe conversion method hydrogen manufacturing, the content of its carbon monoxide is lower, as being that the semi-water gas of raw material contains CO 30～35% with coal or coke; The semi-water gas that makes for the raw material steam reforming with the Sweet natural gas contains CO about 13%; The semi-water gas that makes for the raw material partial oxidation process with the Sweet natural gas contains CO about 20%; With heavy oil is that the water-gas that raw material pure oxygen gasification method makes contains CO about 45～49%.Its shift process mostly is middle change, purified gas is come out for two sections by compressor, enter saturator heating humidification, take the steam of some amount out of, then in mixing tank with additional vapor mixing, make steam: enter after semi-water gas reaches about 1: 1 to be heated in the heat exchanger and enter umformer about 320～350 ℃ and react, umformer has three layers to be divided into two sections, gas temperature raises after one section conversion, at this moment, one section one, introduce the steam controlled temperature between two layers, one section reacted gas temperature continues to raise, one, add steam or the cooling of spray water of condensation between two sections, enter two sections of shift converters about 400～420 ℃, the gas after two sections conversion is drawn by shift converter and is entered interchanger, more than the heating purified gas to 350 ℃, then through water heater heating from the hot water of hot-water tower for saturator usefulness, the conversion gas that is come out by water heater cools off laggard subsequent processing again through cooling tower.
Purifying yellow phosphoric tail gas high density (containing carbon monoxide nearly 90%) CO pressurization conversion is a new technology.Because conversion is a strong exothermal reaction, high concentration CO can produce high temperature, and the too high meeting of temperature causes catalyst to burn; Reaction fierceness under high concentration CO, difficult control of temperature, catalyst is afraid of temperature fluctuation (being not more than ± 5 ℃) most, and temperature fluctuation is too big, reduces catalyst intensity, and easily efflorescence reduces catalyst activity; The reaction heat difficulty or ease shift out, if use steam cooling, then steam consumption is too big, if use the then fragile catalyst of water of condensation spraying cooling; The umformer catalyst number of plies is too many, complex structure, and difficult control of temperature.
And be used for the production of carbon one Chemicals, as dimethyl ether synthesis of synthetic gas or synthesizing methanol, its unstripped gas is H by theoretical proportioning
2/ CO=2 only requires the CO interconversion rate to reach 67% and gets final product.For this reason, the present invention proposes carbon monoxide part converter technique.
(3), summary of the invention:
The method that the purpose of this invention is to provide a kind of preparing hydrogen by part changing of yellow phosphorus tail gas, yellow phosphoric tail gas after purifying is mixed with water vapor, the shift-converter of activator is equipped with in feeding, by the part conversion, make the mixed gas of hydrogen, carbon monoxide and carbonic acid gas, reach the purpose of producing carbon one Chemicals.
Transformationreation principle of the present invention:
Carbon monoxide and water vapor acting generate hydrogen and carbonic acid gas, and its reaction is as follows:
CO+H
2O=CO
2+ H
2+ heat
Can find out from above-mentioned reaction,, will generate the hydrogen of a volume and the carbonic acid gas of a volume if any a volume carbon monoxide and one ponding steam reaction, discharge big calorimetric simultaneously, the consumption of water vapour is big more, and the interconversion rate of carbon monoxide is just high more, and hydrogen output is just high more.
FB(flow block) of the present invention such as Fig. 1: yellow phosphoric tail gas and water vapor after will purifying are mixed in proportion, the some of gas mixture is fed heat exchanger, behind the heating gas mixture, the shift-converter of activator again its feeding is equipped with, another partly directly feeds shift-converter as quench gas, carry out transformationreation, umformer two, adopt indirect heat exchanger between three sections, the heat of two sections conversion gas is passed to the purifying exhausting gas of yellow phosphorus gas of self-purifying system, after two sections conversion gas coolings, enter three sections reactors and proceed transformationreation, make hydrogen at last, the mixing transformation gas of carbon monoxide and carbonic acid gas send subsequent processing after heat exchange.
Technology is finished according to the following steps:
1, unstripped gas is a purifying exhausting gas of yellow phosphorus gas, and its main component is CO 85-92%, CO
22-4%, sulphur, phosphorus, arsenic, fluorine total content are less than 50mg/m
3
2, unstripped gas feeds the mixing tank mixing with water vapor, water vapor: the volume ratio=2.5-2.8 of CO amount in the unstripped gas;
3,85-90% feeds heat exchanger in the gas mixture that mixes, and feeds one section of shift-converter again after being heated 380 ℃, and 10-15% directly feeds shift-converter as quench gas in addition;
4, be provided with one in the shift-converter, two, three sections conversion activator B113 (ferric oxide), 380 ℃ of one section inlet temperatures, 500 ℃ of one section outlet temperature, 420 ℃ of two sections inlet temperatures, 480 ℃ of second stage exit temperature, 390 ℃ of three sections inlet temperatures, 410 ℃ of three sections temperature outs, one section is reacted when temperature is upgraded to 500 ℃, after reducing to 420 ℃ with the one section outlet temperature from 500 ℃, one section outlet feeding quench gas enters two sections, two sections transformationreations are during to 480 ℃ of temperature, after exit gas introducing intermediate heat passes to the purifying exhausting gas of yellow phosphorus gas of self-purifying system with heat, conversion temperature degree feeds three sections transformationreations after reducing to 390 ℃ from 480 ℃ again, and transformationreation is finished when temperature rises to 410 ℃, generates hydrogen, the conversion gas of carbon monoxide and carbonic acid gas.The control of each layer of activator temperature all reaches the purpose of temperature-stable with adjusting cold shock tolerance, process is a continuous production.
5, conversion gas through heat exchanger cooling back the raw material pneumatic transmission subsequent processing as the production of carbon one Chemicals.Total conversion rate 60-75%.
Advantage of the present invention is:
(1), is used for the conversion of high concentration CO gas.
(2), activator is without water of condensation, steam consumption is few, can not produce long-pending shell phenomenon, inorganic salts is few, the catalyst layer resistance is low, the catalyzer long service life.
(3), transformationreation water vapor consumption is few, energy consumption is low, especially purified gas does not need external steam heating, this has also saved steam.
(4), the control of each layer of activator temperature all reaches the purpose of temperature-stable with adjusting cold shock tolerance.
(4), description of drawings: Fig. 1 is a process flow sheet of the present invention.
(5), embodiment:
Embodiment one
1, processing condition
1), unstripped gas (purification yellow phosphoric tail gas) air input 1500Nm
3/ h on average forms CO 89.7%, CO
22.6%, sulphur, phosphorus, arsenic, fluorine total content are less than 50mg/m
3
2), water vapor: volume ratio=2.5 of CO amount in the unstripped gas;
3), adopt the B113 activator, 500 ℃ of one section temperature, 480 ℃ of two sections temperature, 410 ℃ of three sections temperature;
4), activator divides three sections, one, uses the unstripped gas cold shock between two sections, in case catalyst is overheated, after between two, three sections conversion gas being introduced intermediate heat heat being passed to the purifying exhausting gas of yellow phosphorus gas of self-purifying system, conversion gas returns three sections again and continues transformationreations.Conversion gas after the conversion consists of CO 17.95%, CO
239.16%, H
238.2%, shift conversion rate: 67.8%.
2, converter design parameter:
Working pressure: 0.95MPa (gauge pressure)
1200mm, inner lining refractory block 150mm, high H=9800mm in specification: φ outer 1500mm, the
Catalyst divides three sections, one section: three sections of two sections of 600mm: 800mm: 1000mm, all use the B113 activator, catalyst cubic capacity 2.7m
3Catalyst unit weight 1350kg/m
3
Embodiment two
1, processing condition
1), unstripped gas (purification yellow phosphoric tail gas) air input 10000Nm
3/ h on average forms CO 85%, CO
23.5% sulphur, phosphorus, arsenic, fluorine total content are less than 50mg/m
3
2), water vapor: volume ratio=2.8 of CO amount in the unstripped gas;
3), adopt the B113 activator, 500 ℃ of one section temperature, 480 ℃ of two sections temperature, 410 ℃ of three sections temperature;
4), the conversion gas after the conversion consists of CO 17.38%, CO
239.16%, H
236.94%, shift conversion rate: 67.8%.
2, converter design parameter:
Working pressure: 30000Pa
3800mm inner lining refractory block 200mm in the outer 4200mm of specification: φ, high H=9800mm
Activator divides three sections, one section: three sections of two sections of 700mm: 800mm: 1000mm, all use the B113 catalyst, catalyst cubic capacity: 28m
3
Claims (2)
1, a kind of method of preparing hydrogen by part changing of yellow phosphorus tail gas, yellow phosphoric tail gas and water vapor after purifying are mixed in proportion, the some of gas mixture is fed heat exchanger, behind the heating gas mixture, the shift-converter of activator again its feeding is equipped with, another partly directly feeds shift-converter as quench gas, carry out transformationreation, umformer two, adopt indirect heat exchanger between three sections, the heat of two sections conversion gas is passed to the purifying exhausting gas of yellow phosphorus gas of self-purifying system, after two sections conversion gas coolings, enter three sections reactors and proceed transformationreation, make hydrogen at last, the mixing transformation gas of carbon monoxide and carbonic acid gas, it is characterized in that: technology is finished according to the following steps:
1), unstripped gas is purifying exhausting gas of yellow phosphorus gas, its main component is CO 85-92%, CO
22-4%, sulphur, phosphorus, arsenic, fluorine total content are less than 50mg/m
3
2), unstripped gas feeds the mixing tank mixing with water vapor, water vapor: the volume ratio=2.5-2.8 of CO amount in the unstripped gas;
3), 85-90% feeds heat exchanger in the gas mixture that mixes, feed one section of shift-converter again after being heated 380 ℃, 10-15% directly feeds shift-converter as quench gas in addition;
4), be provided with one in the shift-converter, two, three sections conversion activators, 380 ℃ of one section inlet temperatures, 500 ℃ of one section outlet temperature, 420 ℃ of two sections inlet temperatures, 480 ℃ of second stage exit temperature, 390 ℃ of three sections inlet temperatures, 410 ℃ of three sections temperature outs, one section is reacted when temperature is upgraded to 500 ℃, after reducing to 420 ℃ with the one section outlet temperature from 500 ℃, one section outlet feeding quench gas enters two sections, two sections transformationreations are during to 480 ℃ of temperature, after exit gas introducing intermediate heat passes to the purifying exhausting gas of yellow phosphorus gas of self-purifying system with heat, conversion temperature degree feeds three sections transformationreations after reducing to 390 ℃ from 480 ℃ again, and transformationreation is finished when temperature rises to 410 ℃, generates hydrogen, the conversion gas of carbon monoxide and carbonic acid gas.
2, the method for preparing hydrogen by part changing of yellow phosphorus tail gas according to claim 1, it is characterized in that: in order to one, two, three section conversion activator being provided with in the reactor of finishing transformationreation is ferric oxide, one section is 700mm, and two sections is 800mm, and three sections is 1000mm.
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| CNB2005100108407A CN100336715C (en) | 2005-06-07 | 2005-06-07 | Process for preparing hydrogen by part changing of yellow phosphorus tail gas |
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|---|---|---|---|
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| CN100336715C true CN100336715C (en) | 2007-09-12 |
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| CN101787313A (en) * | 2010-03-04 | 2010-07-28 | 昆明理工大学 | Method for preparing artificial natural gas by using high-concentration carbon monoxide smoke |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429764A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | CO isothermal sulfur resistant conversion process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429764A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | CO isothermal sulfur resistant conversion process |
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Granted publication date: 20070912 Termination date: 20100607 |