CN105883807B - Method for purifying carbon dioxide as by-product in magnesite processing - Google Patents
Method for purifying carbon dioxide as by-product in magnesite processing Download PDFInfo
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- CN105883807B CN105883807B CN201610224339.9A CN201610224339A CN105883807B CN 105883807 B CN105883807 B CN 105883807B CN 201610224339 A CN201610224339 A CN 201610224339A CN 105883807 B CN105883807 B CN 105883807B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention provides a method for purifying carbon dioxide as a by-product in magnesite processing. The method comprises the following steps: waste carbon dioxide and oxygen-rich gas are mixed and combusted in a combustion chamber at the combustion temperature of 100-200 DEG C, and combusted carbon dioxide is obtained; combusted carbon dioxide passes through a first filter tower filled with first activated carbon, and first filtered carbon dioxide is obtained; first filtered carbon dioxide passes through a water washing tower, and water washed carbon dioxide is obtained; water washed carbon dioxide passes through an evaporation tower at the evaporation temperature of 60-80 DEG C, and evaporated carbon dioxide is obtained; evaporated carbon dioxide passes through a condensing tower at the condensing temperature of the carbon dioxide liquefaction temperature plus or minus 2 DEG C, and liquid carbon dioxide is obtained; liquid carbon dioxide passes through a second filter tower filled with second activated carbon, and second filtered carbon dioxide is obtained. The method has the advantages that the process is simple, the energy consumption is low, and the food-grade carbon dioxide can be prepared directly from carbon dioxide as the by-product in magnesite processing.
Description
Technical field
The present invention relates to the process technology of magnesite side-product carbon dioxide, more particularly to purification as magnesite
The method of the carbon dioxide of the side-product in ore deposit processing.
Background technology
China's magnesite resource enriches, widely distributed.Can be evaluated whether according to the primary response formula in magnesite fusion process, often
The magnesium oxide finished product of production 1t, will supervene the carbon dioxide of 1.1t.For example, oxygen was produced with Liaoning Province in 2013 only
As a example by changing magnesium products, it is 7.837 × 106t that the province produces magnesium oxide every year, is calculated with this, supervenes 8.661 × 106t dioxies
Change carbon gas, it can be seen that, the annual CO2 emissions of magnesite mining industry are quite huge.However, now with a lot
Mining company during production magnesium oxide, the carbon dioxide by-product that processing is produced through simple dust removal process, directly
Connect and be discharged in air, cause very big ambient pressure.In addition, collecting in some Mining Enterprises, also have to titanium dioxide at present
Carbon carries out trapping technique, wherein uses for example with high-pressure process (8.0MPa), and the method is remained high due to the power consumption of compressor,
Cause to restrict the Main Bottleneck of its development；On the other hand, if adopting low-pressure process (1.6MPa～2.5MPa), the power consumption of compressor
With respect to much smaller, however it is necessary that repeatedly throttling expansion blood pressure lowering to obtain extra cold, there is substantial amounts of energy in throttling process
Loss.
The carbon dioxide composition that magnesite processing is produced composition compared with other sources is relative complex, and existing process is very
Difficult therefrom purification must reach the carbon dioxide of food stage.The carbon dioxide purity for obtaining that main cause is is low, typically has to
To the carbon dioxide of 95 volume % purity, the standard of food stage (99.9) is not reached at all, is not also known exactly which at present
Any composition causes to obtain obtaining food-grade carbon-dioxide from magnesite processed side product carbon dioxide on earth.According to applicant
It is known, there is presently no from magnesite processed side product carbon dioxide direct purification and obtain the report of food-grade carbon-dioxide.
Therefore, be highly desirable at present food stage dioxy can be obtained from magnesite processed side product carbon dioxide direct purification
The method for changing carbon.
The content of the invention
The invention aims to solve magnesite processed side product carbon dioxide cannot direct purification obtain food stage
The technical problem of carbon dioxide.For this purpose, the present inventor gropes research through long-term, there is provided following solution.
Specifically, the invention provides a kind of purification as magnesite processing in side-product carbon dioxide method,
Methods described comprises the steps：
(1) by the CO 2 waste gas processed from magnesite and rich in oxygen gas mix and at 100 DEG C to 200 DEG C
Ignition temperature is burnt in combustor, obtains the carbon dioxide that burns, is wherein maintained at the oxygen rich in oxygen gas
The level of 20 volumes % to 30 volumes % is calculated as with the volume of the waste gas；
(2) make burning carbon dioxide by being filled with the first filtration tank of the first activated carbon, obtain the first filtration titanium dioxide
Carbon；
(3) the first filtering carbon dioxide is made by water scrubber, obtain washing carbon dioxide；
(4) evaporating temperature by washing carbon dioxide at 60 DEG C to 80 DEG C passes through evaporating column, obtains evaporating carbon dioxide；
(5) condensation temperature by evaporation carbon dioxide in co 2 liquefaction temperature to -2 DEG C of co 2 liquefaction temperature is led to
Condensing tower is crossed, liquid CO 2 is obtained；
(6) liquid CO 2 is obtained into the second filtration titanium dioxide by being filled with the second filtration tank of the second activated carbon
Carbon；
Wherein, first activated carbon has 1500m2/ g to 2500m2The surface area of/g, and second activated carbon tool
There is 1200m2/ g to 1600m2The surface area of/g；
Wherein, the aperture in the hole existing for first activated carbon：Mesopore：The volume ratio of macropore is 1:1.0～
2.0:Aperture in 0.4～0.8, and the hole existing for first activated carbon：Mesopore：The volume ratio of macropore is 1:0.6
～0.8:0.2～0.4, wherein described aperture is the hole that aperture is below 5nm, and it is more than 5nm and little that the mesopore is aperture
In the hole of 100nm, the macropore is the hole that aperture is more than 100nm.
The present invention by optimization filtration activated carbon on the basis of, by high-temp combustion, low-temperature evaporation, a step condensation,
Two steps are filtered, relatively low and can be from magnesite processed side product titanium dioxide so as to provide a kind of process is simple, energy consumption
The method that carbon directly prepares food-grade carbon-dioxide.
Description of the drawings
Fig. 1 is technological process of the present invention using magnesite processed side product carbon dioxide purification food-grade carbon-dioxide
Figure.
Specific embodiment
As described above, the invention provides one kind can directly prepare food stage from magnesite processed side product carbon dioxide
The method of carbon dioxide.Methods described can include combustion step, the first filtration step, water-washing step, evaporation step, condensing tower
Step and the second filtration step, these steps can respectively combustor, the first filtration tank, water scrubber, evaporating column, condensing tower and
Second filtration tank is carried out (refer to Fig. 1).
More specifically, methods described comprises the steps：
(1) by the CO 2 waste gas processed from magnesite and rich in oxygen gas mix and at 100 DEG C to 200 DEG C
Ignition temperature is burnt in combustor, obtains the carbon dioxide that burns, is wherein maintained at the oxygen rich in oxygen gas
The level of 20 volumes % to 30 volumes % is calculated as with the volume of the waste gas；
(2) make burning carbon dioxide by being filled with the first filtration tank of the first activated carbon, obtain the first filtration titanium dioxide
Carbon；
(3) the first filtering carbon dioxide is made by water scrubber, obtain washing carbon dioxide；
(4) evaporating temperature by washing carbon dioxide at 60 DEG C to 80 DEG C passes through evaporating column, obtains evaporating carbon dioxide；
(5) condensation temperature by evaporation carbon dioxide in co 2 liquefaction temperature to -2 DEG C of co 2 liquefaction temperature is led to
Condensing tower is crossed, liquid CO 2 is obtained；
(6) liquid CO 2 is obtained into the second filtration titanium dioxide by being filled with the second filtration tank of the second activated carbon
Carbon.
In step (1), mainly by magnesite side-product carbon dioxide (hereinafter sometimes referred to feed carbon dioxide)
Flammable impurity change into gaseous matter.If ignition temperature is too low, it is impossible to obtain with reference to other steps of the inventive method
Carbon dioxide with food stage purity；If temperature is too high, energy consumption is excessive without necessity.
The main purpose of step (2) is the preliminary removing impurity before washing, while avoiding impurity therein from making water scrubber
Even corrode into pollution.
The main purpose of step (3) washes water dissolvable impurity, such as sulfur trioxide, chlorination off using this cheap solvent of water
Hydrogen and fluohydric acid gas are generally by removing with water directly contact.
The main purpose of step (4) is to remove less than 80 DEG C nonvolatile impurity.
The purpose of step (5) is that the other impurities by condensing temperature in carbon dioxide less than carbon dioxide are removed, together
When by co 2 liquefaction in order to store, atmospheric carbon dioxide needs to account for much bigger space after all.
Step (6) is to carry out further purification to liquid carbon dioxide, the inventors discovered that, obtain in step (5)
The purity of liquid CO 2 typically can only achieve 99 volumes % or so, apart from food grade standard (99.9 volume %) or
Fixed gap, in addition, total sulfur content be also unable to reach food stage requirement (volume fraction of total sulfur be 0.1X10-6).Therefore walk
Suddenly (6) are also necessary for the present invention.
The inventors discovered that, in method of the present invention system, being separated by filtration method using two step of activated carbon can be well
The impurity in feed carbon dioxide is removed, to realize the standard of food-grade carbon-dioxide.And, need to make in step (2) and (6)
Filtered with different activated carbons.Wherein, first activated carbon for using in step (2) has 1500m2/ g to 2500m2/
The surface area of g, and second activated carbon has 1200m2/ g to 1600m2The surface area of/g.And, first activated carbon
Aperture in existing hole：Mesopore：The volume ratio of macropore is 1:1.0～2.0:0.4～0.8, the first activated carbon institute
Aperture in the hole of presence：Mesopore：The volume ratio of macropore is 1:0.6～0.8:0.2～0.4, wherein described aperture is aperture
For the hole of below 5nm, it is that, more than 5nm and less than the hole of 100nm, the macropore is that aperture is that the mesopore is aperture
The hole of more than 100nm.
The present invention is had no particular limits to the source of activated carbon and manufacture method, and for example activated carbon can use this area
Known method is manufactured with various carbon raw materials, and for example, activated carbon can be with brown coal, timber, peat and other material with carbon elements
To manufacture.For example, the method for manufacturing activated carbon can include that physically activated (by carbon raw material carbonization and then oxidation) and chemistry are lived
Change.In addition, activated carbon is by being commercially available.Can be using powdered active carbon, granular active carbon and NACF etc.
The activated carbon of form.But, the inventors discovered that, appropriate porosity and hole are constituted, to the highly pure of feed carbon dioxide
What change was a need for.In the present invention, first activated carbon can have 1500m2/g、1600m2/g、1700m2/g、
1800m2/g、1900m2/g、2000m2/g、21000m2/g、2200m2/g、2300m2/g、2400m2/ g or 2500m2/g.Described
Two activated carbons can have 1200m2/g、1300m2/g、1400m2/g、1500m2/ g or 1600m2/g.In addition, described first is active
The aperture in hole existing for charcoal：Mesopore：The volume ratio of macropore is needed for 1:1.0～2.0:0.4～0.8, described first lives
The aperture in hole existing for property charcoal：Mesopore：The volume ratio of macropore is 1:0.6～0.8:0.2～0.4, wherein described aperture
Be aperture be below 5nm hole, it is that, more than 5nm and less than the hole of 100nm, the macropore is aperture that the mesopore is aperture
For the hole of more than 100nm.
In some embodiments, first activated carbon has 1800m2/ g to 2000m2The surface area of/g, and/or institute
State the second activated carbon and there is 1300m2/ g to 1500m2The surface area of/g.
In some embodiments, the activity of first activated carbon and/or second activated carbon for steam activation
Charcoal.
In some embodiments, first activated carbon and/or second activated carbon are independently selected from being lived by peat
Property charcoal, wood activated charcoal, brown coal activated carbon and bituminous coal activated carbon composition group.
In some embodiments, the aperture of first activated carbon：Mesopore：Macropore is 1:1.5:0.6, and be that water steams
The brown coal activated carbon of gas activation.
In some embodiments, the aperture of second activated carbon：Mesopore：Macropore is 1:0.7:0.3, and be that water steams
The peat activated carbon of gas activation.
Activated carbon adsorptive capacity can be characterized using the methylene blue adsorbance level of the activated carbon.In some preferred realities
Apply in mode, first activated carbon has the methylene blue adsorbance of 15g/100g.Other preferred embodiment in,
First activated carbon has the methylene blue adsorbance of 25g/100g.
In some embodiments, the ignition temperature in step (1) is 150 DEG C, and described rich in oxygen gas
Oxygen is calculated as the level of 25 volumes % with the volume of the waste gas.In addition, the evaporating temperature in step (4) is 70 DEG C.
Hereafter the present invention will be further detailed by way of embodiment.
Embodiment 1
By about 500L magnesium oxide is prepared by magnesite during the feed carbon dioxide that produces and isopyknic air
Premixer through being equipped with aerator reaches combustor, and the temperature of combustor is warming up to 150 DEG C and in the temperature
Kept for the time of 10 minutes.The gas for passing through burning is switched to filled with the first activated carbon (purchased from Xianyang letter peak kiln
Equipment company limited) a diameter of 1 meter and height in 5 meters of the first filtration tank, then be switched to a diameter of 1 meter and height is 6
The bottom of towe entrance of the water scrubber of rice (height of water is 5 meters), is connected to from the tower top outlet of water scrubber and has phase with the first filtration tank
In with the condensing tower of size, the condensation temperature of condensing tower is controlled into the liquefaction in co 2 liquefaction temperature to carbon dioxide wherein
Within the temperature range of -2 DEG C of temperature.Then flowing through the liquid CO 2 for obtaining, to be filled with the second activated carbon (salty purchased from Shaanxi
Yang Hongfeng furnace equipments company limited) the second filtration tank (size is the identical of the first filtration tank), so as to obtain final food
Grade carbon dioxide.Method according to GB 10621-2006 is analyzed to liquid CO 2.As a result referring to table 2 below.
Embodiment 2 to 13
In addition to the content described in table 1 below, embodiment 2 to 13 is carried out by the way of same as Example 1.As a result join
See the table below 2.
Table 1
* hole constitutes：Wherein described aperture is the hole that aperture is below 5nm, and it is more than 5nm and little that the mesopore is aperture
In the hole of 100nm, the macropore is the hole that aperture is more than 100nm.
-：Do not detect.
Table 2
From the results shown in Table 2, the inventive method can be manufactured with the carbon dioxide for meeting food grade standard
The volume fraction (10 of volume fraction (%), total sulfur-6), the volume fraction (10 of moisture-6) and oxygen volume fraction (10-6)
Carbon dioxide.
Claims (10)
1. a kind of method of the carbon dioxide of the side-product during purification is processed as magnesite, it is characterised in that methods described bag
Include following steps：
(1) by the CO 2 waste gas processed from magnesite be rich in oxygen gas mix and in 100 DEG C to 200 DEG C of burning
Temperature is burnt in combustor, obtains the carbon dioxide that burns, wherein the oxygen rich in oxygen gas is maintained at institute
The volume for stating waste gas is calculated as the level of 20 volumes % to 30 volumes %；
(2) make burning carbon dioxide by being filled with the first filtration tank of the first activated carbon, obtain the first filtering carbon dioxide；
(3) the first filtering carbon dioxide is made by water scrubber, obtain washing carbon dioxide；
(4) evaporating temperature by washing carbon dioxide at 60 DEG C to 80 DEG C passes through evaporating column, obtains evaporating carbon dioxide；
(5) by evaporation carbon dioxide co 2 liquefaction temperature to -2 DEG C of co 2 liquefaction temperature condensation temperature by cold
Solidifying tower, obtains liquid CO 2；
(6) liquid CO 2 is obtained into the second filtering carbon dioxide by being filled with the second filtration tank of the second activated carbon；
Wherein, first activated carbon has 1500m2/ g to 2500m2The surface area of/g, and second activated carbon has
1200m2/ g to 1600m2The surface area of/g；
Wherein, the aperture in the hole existing for first activated carbon：Mesopore：The volume ratio of macropore is 1:1.0～2.0:0.4
Aperture in～0.8, and the hole existing for second activated carbon：Mesopore：The volume ratio of macropore is 1:0.6～0.8:
0.2～0.4, wherein described aperture is the hole that aperture is below 5nm, and it is more than 5nm and less than 100nm that the mesopore is aperture
Hole, the macropore be aperture be more than 100nm hole.
2. method according to claim 1, it is characterised in that：
Ignition temperature in step (1) is 150 DEG C, and the oxygen rich in oxygen gas is with the stereometer of the waste gas
For the level of 25 volumes %；And/or
Evaporating temperature in step (4) is 70 DEG C.
3. the method according to any one of claim 1 or 2, it is characterised in that first activated carbon has 1800m2/g
To 2000m2The surface area of/g, and/or second activated carbon has 1300m2/ g to 1500m2The surface area of/g.
4. method according to claim 1 and 2, it is characterised in that first activated carbon and/or second activated carbon
For the activated carbon of steam activation.
5. method according to claim 1 and 2, it is characterised in that first activated carbon and/or second activated carbon
Independently selected from the group being made up of peat activated carbon, wood activated charcoal, brown coal activated carbon and bituminous coal activated carbon.
6. method according to claim 1 and 2, it is characterised in that the aperture of first activated carbon：Mesopore：Macropore is
1:1.5:0.6, and be the brown coal activated carbon of steam activation.
7. method according to claim 1 and 2, it is characterised in that the aperture of second activated carbon：Mesopore：Macropore is
1:0.7:0.3, and be the peat activated carbon of steam activation.
8. method according to claim 1 and 2, it is characterised in that first activated carbon has the methylene of 15g/100g
Blue adsorbance.
9. method according to claim 1 and 2, it is characterised in that second activated carbon has the methylene of 25g/100g
Blue adsorbance.
10. method according to claim 1 and 2, it is characterised in that first activated carbon has that 0.4mL/g's is described
Aperture；And/or second activated carbon has the aperture of 0.6mL/g.
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| CN1289720A (en) * | 2000-10-17 | 2001-04-04 | 重庆理想科技有限公司 | Process for preparing food-class high-purity liquid CO2 |
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