CN116395732A - Method and device for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate - Google Patents
Method and device for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate Download PDFInfo
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 26
- WMFHUUKYIUOHRA-UHFFFAOYSA-N (3-phenoxyphenyl)methanamine;hydrochloride Chemical compound Cl.NCC1=CC=CC(OC=2C=CC=CC=2)=C1 WMFHUUKYIUOHRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000018044 dehydration Effects 0.000 title claims abstract description 25
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 17
- 230000008878 coupling Effects 0.000 title claims abstract description 16
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 114
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- 238000004519 manufacturing process Methods 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000002407 reforming Methods 0.000 claims description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 238000005457 optimization Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 8
- 238000007789 sealing Methods 0.000 abstract description 7
- 238000009461 vacuum packaging Methods 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 6
- 239000010453 quartz Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000019771 cognition Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 11
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 229960002713 calcium chloride Drugs 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/30—Concentrating; Dehydrating; Preventing the adsorption of moisture or caking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method and a device for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate, which specifically comprises the following steps: grinding calcium chloride hydrate into powder, placing the powder into a quartz tube, (2) reacting the powder with the calcium chloride hydrate by utilizing a carbon-containing mixed gas at 50-250 ℃ in a contact way, controlling the gas flow to be 1-100 mL/min, and the reaction time to be 0.5-20h, (3) cooling a sample to room temperature in a reaction atmosphere, taking out the sample, collecting the sample by using a vacuum packaging bag, sealing and preserving the sample to obtain an anhydrous calcium chloride product, and (4) collecting the reacted atmosphere to obtain hydrogen. The technology for preparing anhydrous calcium chloride by using the carbon-containing mixed gas and the calcium chloride hydrate through the self-catalytic coupling dehydration establishes a novel theory of the self-catalytic effect of the inorganic salt dehydration based on the basic principle of the coupling self-catalysis, and forms a novel cognition on the dehydration process of the calcium chloride hydrate.
Description
Technical Field
The invention relates to a method and a device for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate.
Background
The anhydrous calcium chloride can be widely applied to the fields of food manufacturing, building materials, medicine, biology and the like, can be used as a drying agent, a dehydrating agent and an antifreezing agent, is also a raw material for producing calcium salt, and is an important chemical reagent in production and life. At present, the most common process method for preparing anhydrous calcium chloride in domestic industry mainly comprises (1) a calcium chloride dihydrate (dehydration method); (2) spray drying dehydration; (3) mother liquor method; (4) a double decomposition method: (5) a refining method. The anhydrous calcium chloride is obtained by heating and drying at high temperature by a dehydration method and a spray drying method, but the energy consumption is high, so that the economic benefit is not great in industrial production, for example, an atomizing nozzle device which is practically used for drying and granulating the anhydrous calcium chloride by a fluidized bed is designed in Chinese patent CN210058176, and the granulation production can be carried out only when the temperature reaches more than 250 ℃; in Chinese patent CN104495903, the mother liquor method for producing calcium chloride realizes waste recycling, but a large amount of steam is consumed for evaporation due to low calcium chloride content of waste liquid, and a large amount of land is occupied by tedding; the double decomposition method is mostly used in areas with byproduct hydrochloric acid, for example, in China patent CN104773750, industrial waste hydrochloric acid is utilized to produce anhydrous calcium chloride, but the cost is higher, and the product competitiveness is low; the refining method has low production cost and good product quality, but has limited resources, and is not suitable for industrial production. Therefore, the existing process for preparing anhydrous calcium chloride with high energy consumption is changed, and the anhydrous calcium chloride is produced in large quantity with low cost and high efficiency by optimizing production conditions, so that the method has important significance.
The water gas shift reaction refers to CO and H 2 O forms CO 2 And H 2 Is a moderately exothermic reaction. Similarly, small carbon-containing molecules such as methanol, methane, ethane, and the like can also be combined with H 2 O generates catalytic reaction in low temperature zone to generate H 2 . If such a process can be coupled with a calcium chloride hydrate dehydration process, calcium chloride is utilized for dehydrationThe transformation coupling reaction of the water product self-catalyzed carbon-containing gas and the crystallization water efficiently occurs in a low-temperature range with thermodynamic advantages, and is expected to reduce the dehydration temperature and simultaneously lead H to be generated 2 Conversion of O to H 2 Improving the economic value of the process. In addition, the carbon-containing mixed gas can be derived from the hydrogen production by reforming methanol and the downstream hydrogen utilization industry, thereby providing a new channel for removing a large amount of carbon monoxide, methanol and other carbon-containing gases in the tail gas of the hydrogen production by reforming methanol in industry.
Disclosure of Invention
The invention provides a method and a device for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate, aiming at the blank of preparing the anhydrous calcium chloride by dehydrating the calcium chloride at a low temperature. The technology greatly reduces the temperature of calcium chloride dehydration, prepares high-purity anhydrous calcium chloride under milder conditions, greatly reduces industrial energy consumption, simultaneously can effectively remove a large amount of CO in the hydrogen production by reforming methanol and the hydrogen utilization industry at the downstream and simultaneously prepares hydrogen, and has higher economic value.
The invention provides a method and a device for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate. The preparation method comprises the following specific steps:
A. using a carbon-containing mixed gas as a raw material, and carrying out deoxidization optimization treatment on the carbon-containing mixed gas to obtain a treated carbon-containing mixed gas;
the carbon-containing mixed gas is at least one selected from methanol, methane, ethane and carbon monoxide, and the rest gas is balance gas, usually selected from N 2 Or inert gas, the mixed gas can be derived from hydrogen production by reforming methanol and hydrogen industry downstream thereof, and the content of the carbon-containing gas is 1-100%.
The deoxidization optimization treatment step specifically uses 401 manganese deoxidizer for deoxidization, wherein the 401 manganese deoxidizer is manganese metal oxide and is applied to deoxidization purification of gases such as nitrogen, inert gases and the like.
B. And C, enabling the carbon-containing mixed gas treated in the step A to contact with calcium chloride hydrate for reaction, then cooling and collecting the carbon-containing mixed gas in the reaction atmosphere to obtain anhydrous calcium chloride, and collecting tail gas to obtain hydrogen.
The calcium chloride hydrate refers to CaCl with two or more crystal water 2 The method comprises the steps of carrying out a first treatment on the surface of the The anhydrous calcium chloride refers to CaCl with less than one crystal water 2 ；
When the treated carbon-containing mixed gas is contacted with calcium chloride hydrate for reaction, the flow rate of the gas is 1mL/min-1000L/min, preferably 10mL/min-100mL/min.
The concentration of the carbon-containing gas after treatment is 1% -100%, the rest gas is balance gas, and the balance gas is usually selected from N 2 Or inert gas, which may be derived from the methanol reforming hydrogen production and downstream hydrogen industry.
In the reaction process, the temperature programming and heating are adopted, the temperature rising rate is 0.1-100 ℃/min, the reaction temperature is 50-250 ℃, preferably 100-200 ℃, and the time is 0.5-20h, preferably 0.5-4h.
In the reaction process, the mixture is cooled to room temperature and is taken out quickly, and the mixture is collected by a vacuum packaging bag and stored in a sealing way.
In the reaction process, the obtained anhydrous calcium chloride contains CaCl 2 The mass fraction of (2) is more than or equal to 96 percent.
In the reaction process, the average hydrogen yield of the calcium chloride hydrate is 10-2000umol/g.
A method for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate is characterized in that the device is as follows: comprises two or three gas cylinders, wherein one of the gas cylinders is balance gas, and the other one or two gas cylinders are carbon-containing gas;
the carbon-containing gas is methane, ethane and carbon monoxide, and the balance gas is N 2 Or an inert gas;
the gas steel cylinder is connected with a deoxidizing device, the deoxidizing device is connected with a reactor, a pressure gauge is arranged in front of and behind the reactor, and a gas collecting tank is arranged behind the reactor.
A method for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate is characterized in that the device is as follows:
when the carbon-containing gas is methanol, two gas cylinders are provided, wherein one of the two gas cylinders is balance gas, and the other one is carbon-containing gas;
methanol liquid passes through a vaporization device and a heat preservation gas circuit to obtain methanol gas;
the gas steel bottle and the heat-preserving gas circuit are connected with a deoxidizing device, the deoxidizing device is connected with a reactor, a pressure gauge is arranged in front of and behind the reactor, and a gas collecting tank is arranged behind the reactor. The preparation method is characterized in that: the invention provides a method and a device for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate, which realize self-catalytic reaction and synergetic dehydration by utilizing the carbon-containing mixed gas for the first time, thereby efficiently preparing the anhydrous calcium chloride. By the method, the temperature for dehydrating the calcium chloride can be effectively reduced, the energy consumption is greatly reduced, and the production cost for preparing the anhydrous calcium chloride is expected to be greatly reduced. In addition, the carbon-containing mixed gas used by the method can be derived from the hydrogen production industry by reforming methanol and the hydrogen utilization industry at the downstream, so that the economic benefit of the method is greatly improved, meanwhile, hydrogen is prepared, a new thought for preparing hydrogen from inorganic matters containing crystal water is developed, and a new channel is provided for removing a large amount of carbon-containing gas in tail gas of the hydrogen production by reforming methanol in industry.
As can be seen from the XRD pattern of fig. 1, anhydrous calcium chloride was successfully prepared;
as can be seen from the EDTA titration analysis of Table 1, caCl in the prepared anhydrous calcium chloride 2 The mass fraction of the catalyst is more than or equal to 96 percent, and meets the first-level requirement of industrial grade.
As can be seen from the analysis of hydrogen production in Table 2, hydrogen can be produced by the present method, and the average hydrogen production amount is 10 to 2000umol/g.
The technology for preparing anhydrous calcium chloride by using the carbon-containing mixed gas and the calcium chloride hydrate through the self-catalytic coupling dehydration establishes a novel theory of the self-catalytic effect of the inorganic salt dehydration based on the basic principle of the coupling self-catalysis, and forms a novel cognition on the dehydration process of the calcium chloride hydrate.
Description of the drawings:
FIG. 1 is XRD spectra of anhydrous calcium chloride prepared in examples 2-5.
FIG. 2 shows the apparatus for preparing anhydrous calcium chloride by dehydration reaction of carbon-containing mixed gas and calcium chloride hydrate.
The specific embodiment is as follows:
the percentages of gases in the examples which follow are by volume.
Example 1
A. Firstly, grinding calcium chloride dihydrate into powder, weighing 0.4g of calcium chloride dihydrate into a quartz tube, heating and vaporizing methanol to obtain methanol gas, introducing carbon monoxide, and carrying out strict deoxidization optimization treatment on reaction gas before entering a tube furnace, namely deoxidizing by using 401 manganese deoxidizing agent;
B. the concentration of the methanol gas in the step A is selected to be 5% CH 3 OH/5％CO/N 2 (balance gas); the gas flow rate is 80mL/min; heating to 200 ℃ at a heating rate of 10 ℃/min, and reacting for 2 hours.
C. And B, cooling the sample in the step B to room temperature in a reaction atmosphere, taking out, collecting and storing in a vacuum packaging bag in a sealing way to obtain an anhydrous calcium chloride product, and collecting the reacted atmosphere to obtain hydrogen.
Example 2
A. Firstly, grinding calcium chloride dihydrate into powder, weighing 0.4g of calcium chloride dihydrate into a quartz tube, introducing methane gas, and strictly obtaining deoxidization optimizing treatment gas by reaction gas before entering a tube furnace, wherein the treatment step is the same as that of example 1;
B. the methane gas concentration in step A was selected to be 20% CH 4 /N 2 (balance gas), the gas flow rate is 40mL/min, the temperature is raised to 50 ℃ at the heating rate of 10 ℃/min, and the reaction time is 6h.
C. And B, cooling the sample in the step B to room temperature in a reaction atmosphere, taking out, collecting and storing in a vacuum packaging bag in a sealing way to obtain an anhydrous calcium chloride product, and collecting the reacted atmosphere to obtain hydrogen.
Example 3
A. Firstly, grinding calcium chloride dihydrate into powder, weighing 0.2g of calcium chloride dihydrate into a quartz tube, introducing carbon monoxide gas, and strictly obtaining deoxidization optimizing treatment gas before entering a tube furnace, wherein the treatment step is the same as that of example 1;
B. concentrating the carbon monoxide gas in step AThe degree of concentration is selected to be 70% CO/N 2 (balance gas); the gas flow rate is 10mL/min; heating to 100 ℃ at a heating rate of 5 ℃/min, and reacting for 4 hours.
C. And B, cooling the sample in the step B to room temperature in a reaction atmosphere, taking out, collecting and storing in a vacuum packaging bag in a sealing way to obtain an anhydrous calcium chloride product, and collecting the reacted atmosphere to obtain hydrogen.
Example 4
A. Firstly, grinding calcium chloride dihydrate into powder, weighing 0.4g of calcium chloride dihydrate into a quartz tube, introducing a carbon monoxide and methane mixed gas, and strictly obtaining deoxidization optimizing treatment gas by reaction gas before entering a tube furnace, wherein the treatment step is the same as that of example 1;
B. mixing the carbon monoxide and methane in the step A at a ratio of 1:1, 15% CO/15% CH 4 /N 2 (balance gas); the gas flow rate is 60mL/min; heating to 200 ℃ at a heating rate of 5 ℃/min, and reacting for 3 hours.
C. And B, cooling the sample in the step B to room temperature in a reaction atmosphere, taking out, collecting and storing in a vacuum packaging bag in a sealing way to obtain an anhydrous calcium chloride product, and collecting the reacted atmosphere to obtain hydrogen.
Example 5
A. Firstly, grinding calcium chloride dihydrate into powder, weighing 0.4g of calcium chloride dihydrate into a quartz tube, introducing a carbon monoxide and ethane mixed gas, and strictly obtaining deoxidization optimizing treatment gas by reaction gas before entering a tube furnace, wherein the treatment step is the same as that of example 1;
B. mixing the carbon monoxide and ethane in the step A at a ratio of 1:1,1% CO/1% C 2 H 6 /N 2 (balance gas); the gas flow rate is 100mL/min; heating to 150 ℃ at a heating rate of 10 ℃/min, and reacting for 8 hours.
C. And B, cooling the sample in the step B to room temperature in a reaction atmosphere, taking out, collecting and storing in a vacuum packaging bag in a sealing way to obtain an anhydrous calcium chloride product, and collecting the reacted atmosphere to obtain hydrogen.
Table 1: anhydrous calcium chloride EDTA titration analysis prepared in examples 1-5
Table 2: examples 1-5 Hydrogen production during the preparation of Anhydrous calcium chloride
Claims (5)
1. A method for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate is characterized by comprising the following steps:
A. using a carbon-containing mixed gas as a raw material, and carrying out deoxidization optimization treatment on the carbon-containing mixed gas to obtain a treated carbon-containing mixed gas; the carbon-containing mixed gas is at least one of methanol, methane, ethane and carbon monoxide, the volume percentage of the carbon-containing gas is 1-100%, and the rest gas is N 2 Or an inert gas;
B. c, enabling the carbon-containing mixed gas treated in the step A to contact and react with calcium chloride hydrate; the gas flow is 1mL/min-100mL/min, the reaction temperature is 50-300 ℃ and the reaction time is 0.5-20h; and then cooling and collecting the mixture under the reaction atmosphere to obtain anhydrous calcium chloride, and collecting tail gas to obtain hydrogen.
2. The method of claim 1, wherein in step B, the mixed gas may originate from the methanol reforming hydrogen production or its downstream hydrogen utilization industry.
3. The method according to claim 1, wherein in the step B, the reaction is performed by heating at a temperature programmed rate of 0.1 to 100 ℃/min.
4. A method for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate is characterized in that the device is as follows: comprises two or three gas cylinders, wherein one of the gas cylinders is balance gas, and the other one or two gas cylinders are carbon-containing gas;
the carbon-containing gas is methane, ethane and carbon monoxide, and the balance gas is N 2 Or an inert gas;
the gas steel cylinder is connected with a deoxidizing device, the deoxidizing device is connected with a reactor, a pressure gauge is arranged in front of and behind the reactor, and a gas collecting tank is arranged behind the reactor.
5. A method for preparing anhydrous calcium chloride by self-catalytic coupling dehydration of carbon-containing mixed gas and calcium chloride hydrate is characterized in that the device is as follows:
when the carbon-containing gas is methanol, two gas cylinders are provided, wherein one of the two gas cylinders is balance gas, and the other one is carbon-containing gas;
methanol liquid passes through a vaporization device and a heat preservation gas circuit to obtain methanol gas;
the gas steel bottle and the heat-preserving gas circuit are connected with a deoxidizing device, the deoxidizing device is connected with a reactor, a pressure gauge is arranged in front of and behind the reactor, and a gas collecting tank is arranged behind the reactor.
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