CN106145112A - A kind of new technology utilizing temperature control conversion to prepare high-purity CO and system - Google Patents
A kind of new technology utilizing temperature control conversion to prepare high-purity CO and system Download PDFInfo
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- CN106145112A CN106145112A CN201610519413.XA CN201610519413A CN106145112A CN 106145112 A CN106145112 A CN 106145112A CN 201610519413 A CN201610519413 A CN 201610519413A CN 106145112 A CN106145112 A CN 106145112A
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- gas
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- purification
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Abstract
The invention discloses a kind of new technology utilizing temperature control conversion to prepare high-purity CO and system, the application includes: the compression of buffer storage, water ring, wet dedusting, gas compression, preliminary purification, double purification, de-CO2Operation, concentrate CO operation, purify CO operation and fill step, the present invention uses the thick unstripped gas that purifies of temperature control conversion to carry out carbon monoxide purification, solve the problem that the methods of purification such as the decomposition of conventionally employed Methanamide, formic acid decomposition are with high costs, purification process is simple, purification precision is high, low cost, easy to use.
Description
Technical field
The present invention relates to carbon monoxide purification technique field, particularly one utilizes temperature control conversion to prepare high-purity CO
New technology and system.
Background technology
In modern industry produces, carbon monoxide is one of important basic material of carbon geochemistry, and it can be used for multiple organic
The production of chemicals, such as formic acid, oxalic acid, acetic acid, acetic anhydride, propanoic acid, acrylate, carboxylate, dimethylformamide, two isocyanides
The synthesis of the organic chemicals such as the unstripped gas of acid esters, Merlon and polyurethane.But, in oxo process organic chemicals kind
While being continuously increased, the isolation technics of carbon monoxide be it is also proposed higher requirement.
The industrial synthesis gas utilizing oil or natural gas via steam transforming or partial oxidation to prepare, or prepared by coal
Water gas or semiwater gas, from these rich in separation and Extraction the admixture of gas of carbon monoxide.Many industrial waste gases, example
As, the blast furnace gas of steel plant and converter gas, the tail gas of non-ferrous metals smelting works, calcium carbide factory and the tail gas of Yellow Phosphorous Plant, synthesis ammonia dress
The ammoniacal copper solution scrubbing generated gas etc. put, all contains substantial amounts of carbon monoxide.In these gases, carbon monoxide usually with hydrogen, nitrogen, first
Alkane, carbon dioxide and steam etc. coexist, and will obtain pure carbon monoxide, it is necessary to separate and purify.
Traditional carbon monoxide purifies and mainly uses the decomposition methods such as Methanamide decomposition, formic acid decomposition, but this method cost
Height, is only suitable for laboratory and consumption use on a small scale, for industrial high-volume carbon monoxide purifies, tool beyond doubt
Huge cost is had to limit and technical limitations.
Summary of the invention
Based on this, for the problems referred to above, it is necessary to propose a kind of new work utilizing temperature control conversion to prepare high-purity CO
Skill and system, the application uses temperature control conversion purification gas to carry out carbon monoxide purification, solves the decomposition of conventionally employed Methanamide, first
The problem that the methods of purification such as acid decomposition are with high costs, purification process is simple, purifies precision high, easy to use.
It is an object of the invention to be achieved through the following technical solutions: one utilizes temperature control conversion to prepare high single oxidation
The new technology of carbon, comprises the following steps:
Buffer storage: calcium carbide stove exhaust is sent in carbon monoxide gas holder and buffer, mix and store；
Water ring compresses: is sent in water ring compressor by the calcium carbide stove exhaust in carbon monoxide gas holder and is forced into 30KPa-
60KPa；
Wet dedusting: the calcium carbide stove exhaust after being compressed by water ring is sent in the packed tower of built-in Pall ring, calcium carbide stove exhaust
Entered by bottom, with packed tower middle and upper part enter cold water carry out counter current contacting, until calcium carbide stove exhaust in dust take off to
20mg//M3Below；
Gas compression: the calcium carbide stove exhaust after wet dedusting is sent in carbon monoxide compressor, makes the carbide after compression
The pressure of furnace exhaust gas is 1.3MPaG-1.5MPaG；
Preliminary purification: calcium carbide stove exhaust is sent into oil removing in the first purification furnace, is re-fed in the second purification furnace defluorinate and de-
Phosphorus processes；
Double purification: the impurity H in removing calcium carbide stove exhaust2S, COS, arsenide and cyanide；
De-CO2Operation: the gas after double purification is sent in PSA-1 equipment and remove CO2Gas；
Concentrate CO operation: CO will be removed2The gas decompression of operation sends into concentration in PSA-2 equipment after 0.5MPaG,
In gas after concentration, CO content is 98%；
Purify CO operation: the gas after concentrating is sent in PSA-3 equipment and purified；
Fill: the gas pressurized after purifying fills to 12MPa.
Preferably, in double purification step, also include step in detailed below:
Calcium carbide stove exhaust after preliminary purification is sent into pre-desulfurizing tower and sloughs impurity H2S；
Then calcium carbide stove exhaust heater via is warming up to 60 DEG C-120 DEG C and enters hydrolysis tower, by impurity CO S hydrolysis
Become H2S, sends into desulfurizing tower and sloughs H after being down to room temperature2S；
Gas after desulfurization is sent in purifying column and sloughs arsenic and cyanide；
Gas being heated to 120 DEG C-200 DEG C entrance degasifiers and carries out deoxidation treatment, the gas after deoxidation enters gas
Liquid/gas separator, removes remaining moisture.
Preferably, the calcium carbide stove exhaust temperature after compression step is set as 0 DEG C-40 DEG C.
A kind of system utilizing temperature control conversion to prepare high-purity CO, including carbon monoxide gas holder, water ring compressor, fills out
Material tower, carbon monoxide compressor, the first purification furnace, the second purification furnace, pre-desulfurizing tower, hydrolysis tower, desulfurizing tower, purifying column, deoxidation
Device, gas-liquid separator, PSA-1 equipment, PSA-2 equipment, PSA-3 equipment, off-gas buffer tank and product compressor, carbon monoxide gas
The outlet of cabinet is connected with water ring compressor by pipeline, and water ring compressor is connected with packed tower, the gas outlet of packed tower and
The gas access of carbonoxide compressor be connected, the gas outlet of carbon monoxide compressor successively with the first purification furnace, second purify
Stove, pre-desulfurizing tower, hydrolysis tower, desulfurizing tower purifying column, degasifier and gas-liquid separator be connected, gas-liquid separator successively with PSA-
1 equipment, PSA-2 equipment are connected with PSA-3 equipment, and PSA-3 equipment is connected with product compressor.
Preferably, it also includes that off-gas buffer tank, described off-gas buffer tank are connected with PSA-2 equipment.
The invention has the beneficial effects as follows:
(1) use the thick unstripped gas that purifies of temperature control conversion to carry out carbon monoxide purification, low cost, solve conventionally employed formyl
The problem that the methods of purification such as amine decomposition, formic acid decomposition are with high costs；
(2) its technique is simple, directly by calcium carbide stove exhaust purification, it is to avoid tradition needs to add other gas
Carry out chemical reaction；
(3) precision is purified high, it is adaptable to the industrialization of large batch of CO (carbon monoxide converter) gas purifies.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes temperature control conversion purification gas to prepare the flow chart of high-purity CO.
Detailed description of the invention
Below in conjunction with the accompanying drawings embodiments of the invention are described in detail.
Embodiment 1:
As it is shown in figure 1, a kind of new technology utilizing temperature control conversion to prepare high-purity CO, comprise the following steps:
S1, buffer storage: calcium carbide stove exhaust is sent in carbon monoxide gas holder and buffer, mix and store；
S2, water ring compress: sent in water ring compressor by the calcium carbide stove exhaust in carbon monoxide gas holder and be forced into 30KPa；
S3, wet dedusting: the calcium carbide stove exhaust after being compressed by water ring is sent in the packed tower of built-in Pall ring, furnace of calcium carbide tail
Gas is entered by bottom, and the cold water entered with packed tower middle and upper part is carried out, until the dust in calcium carbide stove exhaust takes off to 20mg/M3With
Under；
S4, gas compression: the calcium carbide stove exhaust after wet dedusting is sent in carbon monoxide compressor, makes the electricity after compression
The pressure of stone furnace exhaust gas is 1.3MPaG；
S5, preliminary purification: calcium carbide stove exhaust is sent into oil removing in the first purification furnace, be re-fed in the second purification furnace defluorinate and
Dephosphorization treatment；
S6, double purification: the impurity H in removing calcium carbide stove exhaust2S, impurity CO S, arsenide and cyanide；
S7, de-CO2Operation: the gas after double purification is sent in PSA-1 equipment and remove CO2Gas；
S8, concentration CO operation: CO will be removed2The gas decompression of operation is sent in PSA-2 equipment at concentration after 0.5MPaG
Reason, in the gas after concentration, CO content is 98%；
S9, purification CO operation: the gas after concentrating is sent in PSA-3 equipment and purified；
S10, fill: the gas pressurized after purifying fills to 12MPa.
Embodiment 2:
A kind of new technology utilizing temperature control conversion to prepare high-purity CO, comprises the following steps:
S1, buffer storage: calcium carbide stove exhaust is sent in carbon monoxide gas holder and buffer, mix and store；
S2, water ring compress: sent in water ring compressor by the calcium carbide stove exhaust in carbon monoxide gas holder and be forced into 60KPa；
S3, wet dedusting: the calcium carbide stove exhaust after being compressed by water ring is sent in the packed tower of built-in Pall ring, furnace of calcium carbide tail
Gas is entered by bottom, and the cold water entered with packed tower middle and upper part is carried out, until the dust in calcium carbide stove exhaust takes off to 20mg/M3With
Under；
S4, gas compression: the calcium carbide stove exhaust after wet dedusting is sent in carbon monoxide compressor, makes the electricity after compression
The pressure of stone furnace exhaust gas is 1.5MPaG；
S5, preliminary purification: calcium carbide stove exhaust is sent into oil removing in the first purification furnace, be re-fed in the second purification furnace defluorinate and
Dephosphorization treatment；
S6, double purification: the impurity H in removing calcium carbide stove exhaust2S, impurity CO S, arsenide and cyanide；
S7, de-CO2Operation: the gas after double purification is sent in PSA-1 equipment and remove CO2Gas；
S8, concentration CO operation: CO will be removed2The gas decompression of operation is sent in PSA-2 equipment at concentration after 0.5MPaG
Reason, in the gas after concentration, CO content is 98%；
S9, purification CO operation: the gas after concentrating is sent in PSA-3 equipment and purified；
S10, fill: the gas pressurized after purifying fills to 12MPa.
Embodiment 3:
A kind of new technology utilizing temperature control conversion to prepare high-purity CO, comprises the following steps:
S1, buffer storage: calcium carbide stove exhaust is sent in carbon monoxide gas holder and buffer, mix and store；
S2, water ring compress: sent in water ring compressor by the calcium carbide stove exhaust in carbon monoxide gas holder and be forced into 50KPa；
S3, wet dedusting: the calcium carbide stove exhaust after being compressed by water ring is sent in the packed tower of built-in Pall ring, furnace of calcium carbide tail
Gas is entered by bottom, and the cold water entered with packed tower middle and upper part is carried out, until the dust in calcium carbide stove exhaust takes off to 20mg/M3With
Under；
S4, gas compression: the calcium carbide stove exhaust after wet dedusting is sent in carbon monoxide compressor, makes the electricity after compression
The pressure of stone furnace exhaust gas is 1.4MPaG；
S5, preliminary purification: calcium carbide stove exhaust is sent into oil removing in the first purification furnace, be re-fed in the second purification furnace defluorinate and
Dephosphorization treatment；
S6, double purification: the impurity H in removing calcium carbide stove exhaust2S, impurity CO S, arsenide and cyanide；
S7, de-CO2Operation: the gas after double purification is sent in PSA-1 equipment and remove CO2Gas；
S8, concentration CO operation: CO will be removed2The gas decompression of operation is sent in PSA-2 equipment at concentration after 0.5MPaG
Reason, in the gas after concentration, CO content is 98%；
S9, purification CO operation: the gas after concentrating is sent in PSA-3 equipment and purified；
S10, fill: the gas pressurized after purifying fills to 12MPa.
In several of the above embodiments where, outside calcium carbide stove exhaust enters buffer storage in carbon monoxide gas holder, furnace of calcium carbide
Tail gas enters water ring compressor through carbon monoxide gas holder, enters dedusting in packed tower after supercharging, and the gas after dedusting sends into one
Cooling down after carbonoxide compressor compresses, by carbon monoxide compressor gas temperature≤40 DEG C out, gas pressure is
1.3MPaG-1.5MPaG, carbon monoxide compressor gas out is through the first purification furnace oil removing, the second purification furnace defluorinate, de-
After phosphorus processes, then after fine desulfurization process by dry, deoxidation dearsenization process, send into and PSA-1 equipment removes CO2, it is then fed into PSA-2 and sets
The standby CO, the CO of concentration of concentrating, after evacuating pressurization, sends into and purifies CO in PSA-3 equipment, and final products pressurize through compressor
Fill to 12MPaG.
A kind of system utilizing temperature control conversion to prepare high-purity CO, including carbon monoxide gas holder, water ring compressor, fills out
Material tower, carbon monoxide compressor, the first purification furnace, the second purification furnace, pre-desulfurizing tower, hydrolysis tower, desulfurizing tower, purifying column, deoxidation
Device, gas-liquid separator, PSA-1 equipment, PSA-2 equipment, PSA-3 equipment, off-gas buffer tank and product compressor, carbon monoxide gas
The outlet of cabinet is connected with water ring compressor by pipeline, and water ring compressor is connected with packed tower, the gas outlet of packed tower and
The gas access of carbonoxide compressor be connected, the gas outlet of carbon monoxide compressor successively with the first purification furnace, second purify
Stove, pre-desulfurizing tower, hydrolysis tower, desulfurizing tower purifying column, degasifier and gas-liquid separator be connected, gas-liquid separator successively with PSA-
1 equipment, PSA-2 equipment are connected with PSA-3 equipment, and PSA-3 equipment is connected with product compressor.
Water ring compressor, for being forced into 30KPa-60KPa by the calcium carbide stove exhaust in carbon monoxide gas holder.
The gas access of packed tower is bottom packed tower, and packed tower top is provided with cold water mouth spray, is used for removing furnace of calcium carbide
Dust in tail gas.
Carbon monoxide compressor is to use motor-driven piston compressor, and the admission pressure of carbon monoxide compressor is
0.04MPaG, end outlet pressure is 1.5MPaG, and end outlet gas temperature needs to be cooled to less than 40 DEG C.
First purification furnace is mainly used in oil removing, and the second purification furnace is used for defluorinate and dephosphorization, from the outlet of the second purification furnace
About 300Nm is drawn on road3/ h calcium carbide tail gas initially enters pre-desulfurizing tower removing major part H2S, then heater via is warming up to 60-
120 DEG C enter hydrolysis tower, COS major part hydrolysis are become H2S, is down to room temperature and enters desulfurizing tower A removing H2S.Desulfurizing tower includes
Desulfurizing tower A and desulfurizing tower B, and desulfurizing tower B is used for removing unhydrolysed COS and CS2(i.e. inversion absorption type activated carbon), outlet refers to
Mark total sulfur≤0.1ppm；Gas after desulfurization enters purifying column removing arsenic and cyanide, more heated is warming up to 120 DEG C-200 DEG C
Enter deoxidation tower.After deoxidation, gas enters drying unit, removes remaining moisture.Desulfurizing agent, hydrolytic reagent ensure service life >
1 year, decyanation agent, Hydrodearsenic Catalyst and deoxidizer service life > 2 years.Each composition impurity all distinguishes≤0.1ppm.
PSA-1 equipment is mainly used in removing the CO in gas2, it utilizes adsorbent to CO2Strong adsorptivity, by gas
CO2Being removed to below 30ppm, the component such as other CO, H2, N2, CH4 enters PSA-because absorbability is the most weak by adsorption tower
2 equipment carry out concentrating CO operation.The CO that adsorbent is saturated2Regenerated by inverse put, evacuation afterwards.
In PSA-2 equipment concentrates CO unit, utilize the copper-carrying adsorbent strong adsorptivity to CO gas, by the CO in gas
Absorbing, other is such as H2、N2、Ar、CH4The most weak because of absorbability etc. component, and gradually replaced displacement by CO and go out, PSA-2
In equipment, CO is concentrated, then through displacement concentration, finally obtains being concentrated into the CO of 98% in PSA-2 equipment.CO gas passes through
Inverse put, evacuation are sent into PSA-3 equipment again after compressor pressurization (being forced into 0.6MPaG) and are purified CO.Small part is from compressor chamber
Draw and return PSA-2 equipment as displacement gas, the impurity component of remaining in replacing PSA-2 equipment.Absorption waste gas is decompressed to
Send into user's steam generator after 0.06MPaG and do fuel use.
The present invention uses temperature control conversion to carry out carbon monoxide purification, solves the decomposition of conventionally employed Methanamide, formic acid decomposition
The problem with high costs etc. method of purification, its technique is simple, directly by calcium carbide stove exhaust purification, it is to avoid traditional need
Add other gases and carry out chemical reaction, cost-effective, it is adaptable to the industrialization of large batch of CO (carbon monoxide converter) gas purifies.
Embodiment described above only have expressed the detailed description of the invention of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as, it is noted that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.
Claims (5)
1. one kind utilizes the new technology that high-purity CO is prepared in temperature control conversion, it is characterised in that comprise the following steps:
Buffer storage: calcium carbide stove exhaust is sent in carbon monoxide gas holder and buffer, mix and store；
Water ring compresses: is sent in water ring compressor by the calcium carbide stove exhaust in carbon monoxide gas holder and is forced into 30KPa-60KPa；
Wet dedusting: by water ring compress after calcium carbide stove exhaust send into built-in Pall ring packed tower in, calcium carbide stove exhaust by under
Portion enters, and the cold water entered with packed tower middle and upper part carries out counter current contacting, until the dust in calcium carbide stove exhaust takes off to 20mg/M3
Below；
Gas compression: the calcium carbide stove exhaust after wet dedusting is sent in carbon monoxide compressor, makes the furnace of calcium carbide tail after compression
The pressure of gas is 1.3MPaG-1.5MPaG；
Preliminary purification: calcium carbide stove exhaust is sent into temperature control and converts oil removing in the first purification furnace, be re-fed into defluorinate in the second purification furnace
And dephosphorization treatment；
Double purification: the impurity H in removing calcium carbide stove exhaust2S, COS, arsenide and cyanide；
De-CO2Operation: the gas after double purification is sent in PSA-1 equipment and remove CO2Gas；
Concentrate CO operation: CO will be removed2The gas decompression of operation sends into concentration in PSA-2 equipment after 0.5MPaG, concentrates
After gas in the content of CO be 98%；
Purify CO operation: the gas after concentrating is sent in PSA-3 equipment and purified；
Fill: the gas pressurized after purifying fills to 12MPa.
A kind of new technology utilizing temperature control conversion to prepare high-purity CO, it is characterised in that
In double purification step, also include step in detailed below:
Calcium carbide stove exhaust after preliminary purification is sent into pre-desulfurizing tower and sloughs impurity H2S；
Then calcium carbide stove exhaust heater via is warming up to 60 DEG C-120 DEG C and enters hydrolysis tower, impurity CO S hydrolysis is become H2S,
Send into desulfurizing tower after being down to room temperature and slough H2S；
Gas after desulfurization is sent in purifying column and sloughs arsenic and cyanide；
Gas being heated to 120 DEG C-200 DEG C entrance degasifiers and carries out deoxidation treatment, the gas after deoxidation enters gas-liquid and divides
From device, remove remaining moisture.
The most described a kind of new technology utilizing temperature control conversion to prepare high-purity CO, its feature exists
In, set the calcium carbide stove exhaust temperature after compression step as 0 DEG C-40 DEG C.
4. one kind utilizes the system that high-purity CO is prepared in temperature control conversion, it is characterised in that include carbon monoxide gas holder, water ring
Compressor, filler water scrubber, carbon monoxide compressor, the first purification furnace, the second purification furnace, pre-desulfurizing tower, hydrolysis tower, desulfurization
Tower, purifying column, degasifier, gas-liquid separator, PSA-1 equipment, PSA-2 equipment, PSA-3 equipment, off-gas buffer tank and product pressure
Contracting machine, the outlet of carbon monoxide gas holder is connected with water ring compressor by pipeline, and water ring compressor is connected with packed tower, packed tower
Gas outlet be connected with the gas access of carbon monoxide compressor, the gas outlet of carbon monoxide compressor is clean with first successively
Changing stove, the second purification furnace, pre-desulfurizing tower, hydrolysis tower, desulfurizing tower purifying column, degasifier and gas-liquid separator to be connected, gas-liquid is divided
Being connected with PSA-1 equipment, PSA-2 equipment and PSA-3 equipment successively from device, PSA-3 equipment is connected with product compressor.
A kind of system utilizing temperature control conversion to prepare high-purity CO, it is characterised in that it is also
Including off-gas buffer tank, described off-gas buffer tank is connected with PSA-2 equipment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739310A (en) * | 2017-11-16 | 2018-02-27 | 辽宁海德新化工有限公司 | A kind of desulfurization improves product odour device |
| CN107970754A (en) * | 2018-01-15 | 2018-05-01 | 青海盐湖工业股份有限公司 | The reuse means and reuse method of a kind of calcium carbide stove exhaust |
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| JPS5949818A (en) * | 1982-09-13 | 1984-03-22 | Osaka Oxgen Ind Ltd | Method for concentrating carbon monoxide in gaseous mixture containing carbon monoxide by using adsorption method |
| US5096470A (en) * | 1990-12-05 | 1992-03-17 | The Boc Group, Inc. | Hydrogen and carbon monoxide production by hydrocarbon steam reforming and pressure swing adsorption purification |
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
| CN103204470A (en) * | 2013-03-21 | 2013-07-17 | 新疆天业（集团）有限公司 | Gas transformation deep purifying technique for separating and purifying CO and H2 of calcium carbide furnace |
| CN105617817A (en) * | 2016-03-08 | 2016-06-01 | 镇江东辰环保科技工贸有限公司 | Device and method for recycling CO from acetic acid tail gas |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5949818A (en) * | 1982-09-13 | 1984-03-22 | Osaka Oxgen Ind Ltd | Method for concentrating carbon monoxide in gaseous mixture containing carbon monoxide by using adsorption method |
| US5096470A (en) * | 1990-12-05 | 1992-03-17 | The Boc Group, Inc. | Hydrogen and carbon monoxide production by hydrocarbon steam reforming and pressure swing adsorption purification |
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
| CN103204470A (en) * | 2013-03-21 | 2013-07-17 | 新疆天业（集团）有限公司 | Gas transformation deep purifying technique for separating and purifying CO and H2 of calcium carbide furnace |
| CN105617817A (en) * | 2016-03-08 | 2016-06-01 | 镇江东辰环保科技工贸有限公司 | Device and method for recycling CO from acetic acid tail gas |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739310A (en) * | 2017-11-16 | 2018-02-27 | 辽宁海德新化工有限公司 | A kind of desulfurization improves product odour device |
| CN107970754A (en) * | 2018-01-15 | 2018-05-01 | 青海盐湖工业股份有限公司 | The reuse means and reuse method of a kind of calcium carbide stove exhaust |
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