CN111498887A - System and method for producing solid carbonate and solid carbonate - Google Patents
System and method for producing solid carbonate and solid carbonate Download PDFInfo
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- CN111498887A CN111498887A CN202010321989.1A CN202010321989A CN111498887A CN 111498887 A CN111498887 A CN 111498887A CN 202010321989 A CN202010321989 A CN 202010321989A CN 111498887 A CN111498887 A CN 111498887A
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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
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
Abstract
The invention provides a system for producing solid carbonate, which comprises a carbonization device, a gas input device, a liquid input device and a circulating device, wherein the gas input device is used for inputting gas into the carbonization device; and the circulating device is used for circularly conveying at least one of carbonate solid, unreacted liquid and unreacted gas to the upper end of the carbonization device again and entering the carbonization device for circular reaction. The invention also provides a method for producing carbonate solid and carbonate. According to the system, the carbon dioxide gas, the ammonia gas and the liquid form a gas-liquid mixture in the carbonization device and react in the carbonization device in the top-down movement process, so that the reaction generation efficiency can be improved.
Description
Technical Field
The invention relates to the technical field of inorganic chemical industry, in particular to a system and a method for producing solid carbonate and the solid carbonate.
Background
The calcium magnesium ammonium nitrate is a high-efficiency environment-friendly green fertilizer, is suitable for various soils and crops, can loosen the soil, reduce the concentration of active aluminum, reduce the fixation of active phosphorus, improve the resistance of plants to diseases, promote the activity of beneficial microorganisms in the soil, and has good effects on soil properties and plants. Compared with the existing calcium magnesium nitrate fertilizer obtained by simple physical mixing, when the calcium magnesium nitrate fertilizer is applied to the field of fertilizers, the calcium magnesium nitrate fertilizer has better effect on plants than a single calcium fertilizer, a single magnesium fertilizer or the calcium magnesium nitrate fertilizer obtained by simple physical mixing, is more convenient to package, transport and store, has stable quality and convenient application, is widely liked by consumers and is concerned and researched by more and more people in the fertilizer industry.
Phosphorite is the material basis of phosphorus chemical industry, is the important strategic resource of the country, and the phosphorite resource of China is abundant, but the quality of the phosphorite raw ore is not high, and most of the phosphorites are middle-low quality phosphorites. When in use, low-grade phosphorite generates waste liquid and waste residue when extracting phosphate concentrate, and the preparation of calcium magnesium ammonium nitrate from the waste liquid is a common technology at present and is also highly regarded by the industry. However, the existing process for preparing calcium magnesium ammonium nitrate from the waste liquid does not completely utilize the waste liquid, can generate a lot of waste residues, has low raw material utilization rate, can cause certain harm to the environment, has complex procedures, long consumed time and high cost, and is not beneficial to large-scale production.
In addition, the existing common carbonization method of the ammonium nitrate calcium magnesium solution adopts the ammonium carbonate solution, so that the tail gas and the ammonia gas are required to react in the aqueous solution firstly, and then the ammonium carbonate solution and the ammonium nitrate calcium magnesium solution are mixed and react, the operation is complicated, the addition of water in the carbonization process is increased, the burden is increased for the post-treatment, unnecessary waste is caused, and the production cost is increased.
Disclosure of Invention
In view of the above, the present invention provides a system for producing carbonate solids with improved production efficiency. The details are as follows.
A system for producing solid carbonate is characterized by comprising a carbonization device, a gas input device, a liquid input device and a circulating device, wherein the gas input device and the liquid input device are respectively communicated with the carbonization device, the gas input device is used for inputting gas into the carbonization device, and the liquid input device is used for inputting liquid into the carbonization device;
the upper end of the carbonization device comprises a gas input port and a liquid input port, the gas input device is hermetically connected to the gas input port and communicated with the carbonization device, and the liquid input device is hermetically connected to the liquid input port and communicated with the carbonization device;
the gas input device comprises an ammonia gas input pipeline and a carbon dioxide gas input pipeline, the liquid is a liquid containing calcium ions and/or magnesium ions, the ammonia gas and the carbon dioxide gas input into the gas input device and the liquid containing the calcium ions and/or the magnesium ions input into the liquid input device are subjected to gas-liquid mixing at the upper end inside the carbonization device to form a gas-liquid mixture, and the gas-liquid mixture reacts in the carbonization device to generate carbonate solids, liquid which is not completely reacted and gas which is not completely reacted;
the circulating device is used for circularly conveying at least one of the carbonate solid, the liquid which is not completely reacted and the gas which is not completely reacted to the upper end of the carbonization device again and entering the carbonization device for circular reaction.
In a preferred embodiment, the gas input device further comprises a gas mixing channel, the gas mixing channel is connected between the gas input port of the carbonization device and the ammonia gas input pipeline and the carbon dioxide gas input pipeline, and is used for mixing the ammonia gas output by the ammonia gas input pipeline and the carbon dioxide output by the carbon dioxide gas input pipeline and inputting the mixture into the carbonization device.
In a preferred embodiment, a venturi is disposed in the inner chamber of the carbonization device, the venturi being isolated from the inner wall of the carbonization device, the venturi comprising an inlet portion disposed proximate to the gas input port and the liquid input port, a narrow portion disposed distal to the gas input port and the liquid input port, and an outlet portion, the narrow portion being disposed between the inlet portion and the outlet portion;
the gas-liquid mixture moves to the narrow part and the outlet part from the inlet part in sequence, the gas-liquid mixture reacts in the movement process to generate carbonate solid, liquid which is not completely reacted and gas which is not completely reacted, the carbonate solid and the liquid which is not completely reacted are settled to the lower end of the carbonization device to form a solid-liquid mixture, and the gas which is not completely reacted is discharged from the lower end of the outlet part.
In a preferred embodiment, the lower end of the carbonization device is provided with a gas outlet, the gas outlet is connected with a gas output pipeline, and the gas output pipeline is communicated with the gas input device so as to input the unreacted gas into the gas input device again for recycling.
In a preferred embodiment, the bottom of the carbonization device is further provided with a solid-liquid mixture output device, the solid-liquid mixture output device is provided with an output pipeline, the output pipeline is communicated with the upper end of the carbonization device, and the solid-liquid mixture is input into the liquid input port again for recycling.
In a preferred embodiment, the solid-liquid mixture output device comprises a solid-liquid separator, the solid-liquid separator is connected with the output pipeline, the solid-liquid separator is used for separating the solid-liquid mixture into carbonate solids and liquid without complete reaction, the carbonate solids are output to external equipment, and the liquid without complete reaction is input to the liquid input port again through the output pipeline for recycling.
In a preferred embodiment, the time of the cyclic reaction is more than 10 min.
The present invention also provides a method for producing solid carbonate using the system of any one of the above, the method comprising the steps of:
mixing carbon dioxide gas and ammonia gas to obtain mixed gas, and inputting the mixed gas into a carbonization device;
feeding a liquid comprising calcium ions and/or magnesium ions to a carbonization device;
mixing the mixed gas and the liquid containing calcium ions and/or magnesium ions at the upper part in the inner cavity of the carbonization device to form a gas-liquid mixture, wherein the gas-liquid mixture moves from the upper end to the lower end of the carbonization device;
and the gas-liquid mixture moves to the lower end of the carbonization device to form carbonate solid, liquid which is not completely reacted and gas which is not completely reacted, the carbonate solid and the liquid which is not completely reacted are settled to the lower end of the carbonization device to form a solid-liquid mixture, the liquid which is not completely reacted in the solid-liquid mixture is output from the carbonization device and is input into the carbonization device again from the upper part of the carbonization device through a circulating device, the gas which is not completely reacted is output from the carbonization device, and part of the output gas enters the mixed gas again through the circulating device.
In a preferred embodiment, the ammonia gas, the carbon dioxide gas and the liquid containing calcium ions and/or magnesium ions have a molar concentration ratio of flow rate per second of: ammonia gas, carbon dioxide gas and liquid containing calcium ions and/or magnesium ions are 1: 10-1000: 2-10, wherein the molar concentration of the liquid containing calcium ions and/or magnesium ions refers to the molar concentration of calcium ions and/or magnesium ions.
The invention also provides a carbonate solid prepared by the method, wherein the carbonate solid is at least one of magnesium-containing calcium carbonate, calcium carbonate or magnesium carbonate.
The invention has the beneficial effects that: according to the system, the carbon dioxide gas, the ammonia gas and the liquid form a gas-liquid mixture in the carbonization device and react in the carbonization device in the top-down movement process, so that the reaction generation efficiency can be improved.
Drawings
Fig. 1 is a system for producing carbonate solids according to the present invention.
Fig. 2 is a flow chart of a method for producing solid carbonate according to the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may or may not be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
Referring to fig. 1, an embodiment of the present invention provides a system 10 for producing solid carbonate, where the system 10 includes a carbonization device 100, a gas input device 200 and a liquid input device 300, and a circulation device (not shown), the gas input device 200 and the liquid input device 300 are respectively communicated with the carbonization device 100, the gas input device 200 is used for inputting gas into the carbonization device 100, and the liquid input device 300 is used for inputting liquid into the carbonization device 100.
The upper end of the carbonization device 100 comprises a gas input port 110 and a liquid input port 120, the gas input device 200 is hermetically connected to the gas input port 110 and communicated with the carbonization device 100, and the liquid input device 300 is hermetically connected to the liquid input port 120 and communicated with the carbonization device 100. The gas input device 200 and the liquid input device 300 are arranged at the upper end of the carbonization device 10, which is beneficial to fully mixing the gas output from the gas input device 200 and the liquid output from the liquid input device 300 into a shape of fog under the action of gravity, so as to improve the contact area of the gas and the liquid and improve the reaction generation efficiency.
The gas input device 200 comprises an ammonia gas input pipeline 210 and a carbon dioxide gas input pipeline 220, the liquid is a liquid containing calcium ions and/or magnesium ions, the ammonia gas and the hydrogen dioxide gas input into the gas input device 200 and the liquid containing calcium ions and/or magnesium ions input into the liquid input device 300 are subjected to gas-liquid mixing at the upper end inside the carbonization device 100 to form a gas-liquid mixture; the gas-liquid mixture reacts in the carbonizing apparatus 100 to produce carbonate solid, liquid that has not completely reacted, and gas that has not completely reacted. Wherein the ammonia gas input pipeline 210 is used for inputting the ammonia gas, and the carbon dioxide gas input pipeline 220 is used for inputting carbon dioxide gas. The liquid containing calcium ions and/or magnesium ions is preferably a calcium nitrate solution and/or a magnesium nitrate solution, and the term "calcium nitrate solution and/or magnesium nitrate solution" means that the nitrate solution may be a solution containing calcium nitrate, a solution containing magnesium nitrate, or a solution containing calcium nitrate and magnesium nitrate. And reacting ammonia gas and carbon dioxide gas with the calcium nitrate solution and/or the magnesium nitrate solution to generate calcium carbonate and/or magnesium carbonate solid. In the present invention, the reaction process is that in the inner space of the carbonization device 100, gas and liquid are mixed to form a gas-liquid mixture and react while moving from the upper end to the lower end of the carbonization device 100.
The circulating device is used for circularly conveying at least one of the carbonate solid, the liquid which is not completely reacted and the gas which is not completely reacted to the upper end of the carbonization device 100 again and entering the carbonization device for circular reaction. The circulating device in the invention can recycle the reacted substances of the gas-liquid mixture, thereby improving the utilization rate of calcium ions and/or magnesium ions in the liquid. Preferably, the time of the cyclic reaction is more than 10 min. More preferably, the time of the circulating reaction is 15-30min, so that the energy consumption can be saved and the production time can be shortened under the condition of ensuring the circulating efficiency. In this application, the circulation device comprises a reflux pump.
In the present application, it is preferable that both the carbonate solid and the liquid which is not completely reacted are recycled into the carbonization device 100 for re-reaction, in this case, the carbonization device 100 includes three forms of solid, liquid and gas, the solid is the carbonate solid, the liquid is the liquid which is not completely reacted, the gas is the gas input from the gas input device 200, the three phases are mixed together, the reaction yield can be improved, when the carbonate solid participates in the reaction of the gas-liquid mixture, the carbonate in the solid phase can provide a reaction interface for the reaction of the liquid containing calcium ions and/or magnesium ions with carbon dioxide and ammonia gas, and further, the conversion rate of the calcium ions and magnesium ions in the liquid can be improved, thereby improving the utilization rate of the calcium ions and/or magnesium ions in the liquid.
Wherein, the carbon dioxide gas is derived from the tail gas of phosphorite calcination. In a further embodiment, the phosphorite calcination tail gas is obtained by washing the calcination tail gas generated by phosphoric acid calcination with water; preferably, the content of carbon dioxide in the phosphorite calcining tail gas is more than 80 wt.%, and is preferably more than or equal to 90 wt.%.
The system 10 of the present invention can improve the reaction generation efficiency by reacting the carbon dioxide gas, the ammonia gas, and the liquid in the carbonization device 100 to form a gas-liquid mixture in a top-down movement process in the carbonization device 100.
In a further embodiment, the gas input device 200 further comprises a gas mixing channel 230, and the gas mixing channel 230 is connected between the gas input port 110 of the carbonization device 100 and the ammonia gas input pipeline 210 and the carbon dioxide gas input pipeline 220, and is used for mixing the ammonia gas output by the ammonia gas input pipeline 210 and the carbon dioxide output by the carbon dioxide gas input pipeline 220 and inputting the mixture into the carbonization device 100. The carbon dioxide gas and the ammonia gas are mixed in the gas mixing passage 230 and then enter the carbonizing device 100.
In a further embodiment, a venturi 400 is provided in the inner cavity of the carbonization device 100, and the venturi 400 is isolated from the inner wall of the carbonization device 100. That is, the venturi tube 400 is disposed in the middle of the carbonizing apparatus 100 and may be fixed in the carbonizing apparatus 100 by a holder. The venturi 400 includes an inlet portion 410, a narrowed portion 420, and an outlet portion 430, the inlet portion 410 being disposed proximate to the gas input port 110 and the liquid input port 120, the outlet portion 430 being disposed distal to the gas input port 110 and the liquid input port 120, the narrowed portion 420 being disposed between the inlet portion 410 and the outlet portion 430. Wherein the inner diameter of the narrow portion 420 is smaller than the inner diameters of the inlet portion 410 and the outlet portion 430.
The gas-liquid mixture Q moves from the inlet part 410 to the narrow part 420 and the outlet part 430 in sequence, the gas-liquid mixture Q reacts during the movement to generate carbonate solid, liquid which is not completely reacted, and gas which is not completely reacted, the carbonate solid and the liquid which is not completely reacted settle to the lower end of the carbonization device 100 to form a solid-liquid mixture, and the gas which is not completely reacted goes out from the lower end of the outlet part 430.
The venturi tube 400 in the invention can further mix the gas and the liquid in the gas-liquid mixture Q, can ensure the efficient and sufficient mixing of the two phases, and has the advantages of simple structure, low energy consumption, less equipment investment and convenient maintenance.
In some embodiments, the unreacted gas or the gas-liquid mixture Q moves from the lower end of the carbonization device 100 to the upper end of the carbonization device 100 along the inner cavity between the venturi tube 400 and the inner wall of the carbonization device 100 until entering the inlet portion 410 of the venturi tube 400 again, so as to circulate, thereby improving the production efficiency of carbonate.
In a further embodiment, the lower end of the carbonization device 100 is provided with a gas outlet 130, the gas outlet 130 is connected with a gas output pipeline 140, and the gas output pipeline 140 is communicated with the gas input device 200, so that the gas which is not completely reacted is input into the gas input device 200 again for recycling. In the present invention, the utilization rate of the gas can be improved by feeding the unreacted gas to the gas feeding device 200 again and then feeding the gas to the carbonizing device 100 for reuse.
In a further embodiment, a solid-liquid mixture output device 150 is further arranged at the bottom of the carbonization device 100, the solid-liquid mixture output device 150 is provided with an output pipeline 160, the output pipeline 160 is communicated with the upper end of the carbonization device 100, and the solid-liquid mixture is input into the liquid input port 120 again for recycling. The solid-liquid mixture may be a solid-liquid mixture remaining after a part of the solids are separated by solid-liquid separation, or the solid-liquid mixture may be directly input to the liquid input port 120 through the output pipeline 160 for recycling, so that the effective reaction of the components in the liquid is complete, and the production efficiency is improved.
In other embodiments, the liquid that has not completely reacted is mixed with the liquid containing calcium ions and/or magnesium ions, and then mixed with carbon dioxide gas and ammonia gas after being introduced into the carbonization device 100 through the liquid introduction device 300.
In a further embodiment, a reflux pump 170 is added between the solid-liquid mixture outlet device 150 and the outlet line 160, and the reflux pump 170 delivers the solid-liquid mixture into the liquid inlet 120.
In a further embodiment, the solid-liquid mixture output device 150 comprises a solid-liquid separator (not shown) connected to the output pipeline 160, the solid-liquid separator is used for separating the solid-liquid mixture into carbonate solids and liquid without complete reaction, the carbonate solids are output to the external equipment 20, and the liquid without complete reaction is input to the liquid input port 120 again through the output pipeline 160 for recycling. In this embodiment, there are two output pipelines 160, one of the output pipelines 160 is connected to the liquid input port 300, and the return pump 170 is connected to the output pipeline 160; another output line 160a communicates with the external equipment 20 for outputting carbonate solids to the external equipment 20.
The system 10 is preferably applied to a process for preparing magnesium-containing calcium carbonate from phosphorite, and the system 10 is provided for solving the problems of complex reaction process, troublesome operation, high water addition amount in the carbonization process, low raw material utilization rate, high cost and the like of the conventional preparation process of the magnesium-containing calcium carbonate. This system 10 is mainly with gas and liquid in letting in carbonizing apparatus 100, and wherein gas includes phosphorite calcination tail gas and ammonia, and the liquid is the nitrate solution that contains calcium nitrate solution and/or magnesium nitrate solution, and in carbonizing apparatus 100, phosphorite calcination tail gas, ammonia and nitrate solution fully mix, carry out the carbonization reaction, obtain magnesium-containing calcium carbonate. Wherein the magnesium-containing calcium carbonate is one of the solid carbonates in the invention, and the magnesium-containing calcium carbonate is the combination of magnesium carbonate and calcium carbonate. In other embodiments, the solid carbonate further comprises one of calcium carbonate or magnesium carbonate.
The system 10 of the invention can ensure that calcium and magnesium ions in the nitrate solution are fully carbonized and not wasted, and the utilization rate of raw materials is high; the introduction of extra water into the system is avoided, unnecessary waste is reduced, the burden of subsequent treatment is reduced, and the energy consumption is low; the carbon dioxide in the calcination tail gas generated by phosphorite calcination can be fully utilized, the exhaust emission is reduced, the environmental pollution is avoided, the raw material cost is reduced, the resource utilization of the material is realized, and the remarkable economic benefit and the environmental protection benefit are achieved.
The system 10 disclosed by the invention is simple to operate, easy to implement and low in cost, the prepared magnesium-containing calcium carbonate contains rich nitrogen (N), calcium (Ca) and magnesium (Mg) elements, can be directly used as a liquid fertilizer to be applied to crops, or can be used as donors of the N, Mg and Ca in the preparation of the liquid fertilizer to be added into the production and preparation of the liquid fertilizer, so that the cost of liquid fertilizer raw materials can be saved, the nutrition supplement and absorption of the crops are facilitated, and the system has a good application value and is easy to popularize and apply.
The "calcium nitrate solution and/or magnesium nitrate solution" may be a solution containing calcium nitrate, a solution containing magnesium nitrate, or a solution containing calcium nitrate and magnesium nitrate.
Preferably, the nitrate solution is a nitrate solution comprising a calcium nitrate solution and a magnesium nitrate solution. The nitrate solution containing the calcium nitrate solution and the magnesium nitrate solution is subjected to a carbonization reaction with the phosphorite calcining tail gas and ammonia gas to generate the required calcium ammonium nitrate and magnesium ammonium nitrate, so that the synergistic effect is fully exerted, the growth of crops and the supplement of calcium and magnesium elements are facilitated, and the quality of the crops is obviously improved.
In a preferred embodiment, the phosphorite calcination tail gas is obtained by washing the calcination tail gas generated by phosphoric acid calcination with water.
Preferably, the content of carbon dioxide in the tail gas is > 80 wt.%, preferably ≥ 90 wt.%.
According to the invention, the tail gas of phosphorite calcination is gas containing carbon dioxide which is washed by water to remove most of ash. It can be understood that the calcination tail gas generated by the phosphorite calcination contains a certain amount of ash, impurities and carbon dioxide, and the carbon dioxide is mainly used for reacting with ammonia gas and nitrate in the carbonization reaction, so that the tail gas is required to be purified firstly when the phosphorite calcination tail gas is used, most of the impurities or ash are removed, gas mainly containing carbon dioxide is obtained, and then the carbonization reaction is carried out.
It should be noted that the present invention is not limited to specific types of phosphorite, specific calcining modes, etc., and for example, the middle-low grade phosphorite may be calcined to obtain a pyrolysis product and a calcination tail gas containing carbon dioxide. The specific washing conditions of the calcination tail gas are not particularly limited, and the purpose of the present invention is not limited as long as most of the ash can be removed to obtain a tail gas containing a suitable content of carbon dioxide.
Preferably, the carbon dioxide content in the tail gas after water washing purification is more than 80 wt.%.
In a preferred embodiment, the present invention employs the venturi 400 as a gas-liquid mixer to further mix the gas and liquid.
The gas-liquid mixer adopting the Venturi tube structure is convenient for adjusting the proportion of gas and liquid in the gas-liquid mixture, can ensure efficient and sufficient mixing of two phases, and has the advantages of simple structure, low energy consumption, low equipment investment and convenient maintenance.
In a preferred embodiment, the phosphorite calcination tail gas, the ammonia gas and the nitrate solution are subjected to carbonization reaction in the carbonization device 100 to obtain a solid-liquid mixture and gas which is not completely reacted, and the solid-liquid mixture is conveyed to the liquid input port 120 of the carbonization device 100 to be subjected to circulating carbonization to obtain magnesium-containing calcium carbonate. The solid-liquid mixture comprises magnesium carbonate and calcium carbonate solids and liquid which is not completely reacted.
Preferably, in the circulating carbonization process, the solid-liquid mixture is firstly mixed with the nitrate solution and then mixed with the phosphorite calcination tail gas and the ammonia gas.
Preferably, the solid-liquid mixture is delivered to the inlet of the carbonization device 100 using a reflux pump 170.
According to the present invention, the gas and the liquid are introduced into the carbonization device 100 and then react to generate a solid-liquid mixture, the solid-liquid mixture is subjected to cyclic carbonization, that is, the generated solid-liquid mixture is mixed again, and the solid-liquid mixture is mixed with the liquid and then mixed with the gas during the re-mixing process. Therefore, the full carbonization of the nitrate solution can be ensured, the carbon dioxide in the tail gas is fully utilized, the utilization rate of the raw materials can be improved, the introduction of extra moisture in the system is avoided, the cost is reduced, and the waste is reduced.
Further, the method comprises the following steps: (1) liquid feeding: delivering the nitrate solution to the liquid input port 120 of the carbonator 100; (2) mixing, namely respectively introducing the phosphorite calcining tail gas and ammonia gas into the gas input port 110 of the carbonizing device 100, and mixing the phosphorite calcining tail gas and the ammonia gas with the nitrate solution at the narrow part 420 of the Venturi tube 400 to form a gas-liquid mixture; (3) carbonizing: carrying out carbonization reaction on the gas-liquid mixture in the Venturi tube 400 to obtain a solid-liquid mixture; (4) refluxing or circulating carbonization: the solid-liquid mixture is conveyed from the solid-liquid mixture output device 150 of the carbonization device 100 to the liquid input port 120 of the carbonization device 100 by the reflux pump, and enters the venturi tube 400 again for cyclic carbonization, so that magnesium-containing calcium carbonate is obtained.
In a further embodiment, the ammonia gas, the carbon dioxide gas and the liquid comprising calcium ions and/or magnesium ions have a molar concentration ratio of flow per second of: ammonia gas, carbon dioxide gas and liquid containing calcium ions and/or magnesium ions are 1: 10-1000: 2-10, wherein the molar concentration of the liquid containing calcium ions and/or magnesium ions refers to the molar concentration of calcium ions and/or magnesium ions. The liquid containing calcium ions and/or magnesium ions is a mixed liquid of magnesium nitrate and calcium nitrate.
In this example, the mass concentration of the nitrate solution entering the carbonator 100 is 0.26 tons per ton of water per unit time. In other embodiments, the mass concentration of the nitrate solution entering the carbonator 100 is between 0.1 and 0.25 tons per ton of water per unit time.
Referring to fig. 2, the present invention further provides a carbonization method using any one of the above systems, wherein the carbonization method comprises the following steps S100, S200 and S300.
Step S100, mixing the carbon dioxide gas and the ammonia gas to obtain a mixed gas, and inputting the mixed gas to the carbonization device 100. The carbonizing apparatus 100 is as described in the foregoing embodiments, and a description thereof will not be repeated. The carbon dioxide gas is preferably phosphorite calcination tail gas.
In step S200, a liquid containing calcium ions and/or magnesium ions is input to the carbonization device 100. In the present embodiment, the liquid containing calcium ions and/or magnesium ions is preferably a mixed liquid of calcium nitrate and magnesium nitrate.
Step S300, mixing the mixed gas and the liquid containing calcium ions and/or magnesium ions at an upper portion in the inner cavity of the carbonization device 100 to form a gas-liquid mixture, wherein the gas-liquid mixture moves from an upper end to a lower end of the carbonization device 100. Preferably, the mixing is performed from the venturi 400 in the carbonizing apparatus 100, as described above, and a description thereof will not be repeated.
The gas-liquid mixture moves to the lower end of the carbonization device 100 to form carbonate solids, liquid which is not completely reacted, and gas which is not completely reacted, the carbonate solids and the liquid which is not completely reacted settle to the lower end of the carbonization device 100 to form a solid-liquid mixture, the liquid which is not completely reacted in the solid-liquid mixture is output from the carbonization device 100 and is input into the carbonization device 100 again from the upper part of the carbonization device 100 through a circulating device, the gas which is not completely reacted is output from the carbonization device 100, and part of the output gas is input into the mixed gas again through the circulating device. The specific method of recycling is as described above.
In a further embodiment, the ammonia gas, the carbon dioxide gas and the liquid comprising calcium ions and/or magnesium ions have a molar concentration ratio of flow per second of: ammonia gas, carbon dioxide gas and liquid containing calcium ions and/or magnesium ions are 1: 10-1000: 1-10, wherein the molar concentration of the liquid containing calcium ions and/or magnesium ions refers to the molar concentration of calcium ions and/or magnesium ions. In the invention, the using amount of the carbon dioxide gas is far larger than that of ammonia gas and liquid containing calcium ions and/or magnesium ions, so that the forward movement of the reaction can be promoted, the generation of carbonate solid is accelerated, and the production efficiency of the carbonate solid is improved.
In a further embodiment, after the cyclic carbonization, the method further comprises terminating the reaction, wherein no additional water or other reaction solvent is added in the method, and the terminating reaction is determined by: and when detecting that the concentration of the solute in the liquid which is not completely reacted in the solid-liquid mixture output device 150 after the first time reaction is less than 10% of the concentration of the solute in the liquid which enters the liquid input device 300 for the first time, and the difference between the concentrations of the solute in the liquid which is not completely reacted in the solid-liquid mixture output device 150 after the first time reaction and the second time reaction is less than 10% of the concentration of the solute in the liquid which is not completely reacted in the solid-liquid mixture output device 150 after the first time reaction, determining the termination time of the second time termination reaction. Wherein the first time and the second time are separated by 1-10min, and the second time is after the first time. The concentration of the solute in the liquid which is not completely reacted in the solid-liquid mixture output device 150 can be monitored in real time by a concentration monitor to assist in judging the termination time of the carbonization reaction.
In a further embodiment, the temperature at which the reaction is maintained in the carbonization unit is between 25 and 100 ℃, preferably 30 ℃. The reaction time is 10-90min, preferably 30 min.
In the present invention, the source of the ammonia gas and nitrate solution is not particularly limited, and various raw materials known to those skilled in the art may be used; if it is commercially available, it can be prepared by itself by a method known to those skilled in the art.
The preparation method of the magnesium-containing calcium carbonate provided by the invention has the advantages of simple process and low cost, the prepared magnesium-containing calcium carbonate is a solution containing rich nitrogen, magnesium and calcium elements, can be directly used as a liquid fertilizer to be applied to crops, and can also be used as a donor of the nitrogen, magnesium and calcium elements in the liquid fertilizer preparation to be added into the production and preparation of the liquid fertilizer, so that the raw material cost of the liquid fertilizer can be saved, the nutrition supplement and absorption of the crops are facilitated, the soil structure is improved, and the crop quality is improved.
The invention also provides a carbonate solid prepared by the method, wherein the carbonate solid is at least one of magnesium-containing calcium carbonate, calcium carbonate or magnesium carbonate. Preferably, the magnesium-containing calcium carbonate is granulated to obtain magnesium-containing calcium carbonate particles.
The magnesium-containing calcium carbonate is granulated to obtain solid granular calcium magnesium ammonium nitrate, is convenient to transport, can be directly used as a fertilizer to act on plants, and provides a large amount of elements necessary for the plants.
The invention also provides a preparation method of the magnesium-containing calcium carbonate and application of the magnesium-containing calcium carbonate or the magnesium-containing calcium carbonate in preparation of fertilizers.
It should be understood that the application of the present invention is based on the same inventive concept as the aforementioned preparation method of magnesium-containing calcium carbonate, and the magnesium-containing calcium carbonate or the application of the magnesium-containing calcium carbonate, and thus has at least the same advantages as the aforementioned preparation method of magnesium-containing calcium carbonate, and will not be described herein again.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
A method for producing magnesium-containing calcium carbonate solids using the system 10 of the above example, comprising the steps of:
respectively introducing the phosphorite calcination tail gas, ammonia gas and nitrate solution into a carbonization device 10 for carbonization reaction, wherein the nitrate solution is nitrate solution containing calcium nitrate solution and magnesium nitrate solution, carrying out carbonization reaction to obtain solid-liquid mixture, conveying the solid-liquid mixture to an inlet of a gas-liquid mixing device by using a reflux pump, carrying out circulating carbonization, and mixing the solid-liquid mixture with the nitrate solution firstly and then with the phosphorite calcination tail gas and ammonia gas to obtain magnesium-containing calcium carbonate. In example 1, the mass concentration of the nitrate solution is 0.26 ton/ton water per hour, and in this example, 27 tons of nitrate solution, specifically, 7 tons of nitrate solution dissolved in 20 tons of water, are added, wherein the mass ratio of calcium nitrate and magnesium nitrate is 1: 1. In other embodiments, the mass ratio of calcium nitrate to magnesium nitrate is not limited. According to the molar concentration ratio, the ammonia gas, the carbon dioxide gas and the nitrate solution are 1: 800: 3, wherein the content of the carbon dioxide gas in the phosphorite calcining tail gas is 92 wt.%.
The system and the method are adopted to produce the magnesium-containing calcium carbonate solid, and the circulating reaction is carried out to finally obtain 3.83 tons of the magnesium-containing calcium carbonate solid, the theoretical production value is 4.12 tons, and the production efficiency is 93 percent.
Example 2
A method for producing magnesium-containing calcium carbonate solids using the system 10 of the above example, comprising the steps of:
respectively introducing the phosphorite calcination tail gas, ammonia gas and nitrate solution into a carbonization device 10 for carbonization reaction, wherein the nitrate solution is nitrate solution containing calcium nitrate solution and magnesium nitrate solution, carrying out carbonization reaction to obtain solid-liquid mixture, conveying the solid-liquid mixture to an inlet of a gas-liquid mixing device by using a reflux pump, carrying out circulating carbonization, and mixing the solid-liquid mixture with the nitrate solution firstly and then with the phosphorite calcination tail gas and ammonia gas to obtain magnesium-containing calcium carbonate. In example 2, the mass concentration of the nitrate solution was 0.22 ton/ton water per hour, and in this example 27 tons of nitrate solution, specifically 7 tons of nitrate solution dissolved in 20 tons of water, were added, wherein the mass ratio of calcium nitrate and magnesium nitrate was 1: 1.01. According to the molar concentration ratio, the ammonia gas, the carbon dioxide gas and the nitrate solution are 1: 600: 5, wherein the content of the carbon dioxide gas in the phosphorite calcining tail gas is 92 wt.%.
The system and the method are adopted to produce the magnesium-containing calcium carbonate solid, and the circulating reaction is carried out to finally obtain 3.72 tons of the magnesium-containing calcium carbonate solid, the theoretical production value is 4.12 tons, and the production efficiency is 90.3 percent.
Example 3
A method for producing magnesium-containing calcium carbonate solids using the system 10 of the above example, comprising the steps of:
respectively introducing the phosphorite calcination tail gas, ammonia gas and nitrate solution into a carbonization device 10 for carbonization reaction, wherein the nitrate solution is nitrate solution containing calcium nitrate solution and magnesium nitrate solution, carrying out carbonization reaction to obtain solid-liquid mixture, conveying the solid-liquid mixture to an inlet of a gas-liquid mixing device by using a reflux pump, carrying out circulating carbonization, and mixing the solid-liquid mixture with the nitrate solution firstly and then with the phosphorite calcination tail gas and ammonia gas to obtain magnesium-containing calcium carbonate. In example 3, the mass concentration of the nitrate solution was 0.26 ton/ton water per hour, and in this example 27 tons of nitrate solution, specifically 7 tons of nitrate solution dissolved in 20 tons of water, were added, wherein the mass ratio of calcium nitrate and magnesium nitrate was 1.1: 1. According to the molar concentration ratio, the ammonia gas, the carbon dioxide gas and the nitrate solution are 1: 900: 4, wherein the content of the carbon dioxide gas in the phosphorite calcining tail gas is 92 wt.%.
The system and the method are adopted to produce the magnesium-containing calcium carbonate solid, and the circulating reaction is carried out to finally obtain 3.95 tons of the magnesium-containing calcium carbonate solid, the theoretical production value is 4.12 tons, and the production efficiency is 95.9 percent.
Comparative example 1
Comparative example 1 the same amount of phosphorite calcination tail gas, ammonia gas and nitrate solution in example 1 were introduced into a conventional reactor, and finally 2.98 tons of magnesium-containing calcium carbonate solid was obtained by production, the theoretical production value was 4.12 tons, and the production efficiency was 72%. It can be seen that the system and method for producing carbonate solids provided by the present invention can improve production efficiency.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A system for producing solid carbonate is characterized by comprising a carbonization device, a gas input device, a liquid input device and a circulating device, wherein the gas input device and the liquid input device are respectively communicated with the carbonization device, the gas input device is used for inputting gas into the carbonization device, and the liquid input device is used for inputting liquid into the carbonization device;
the upper end of the carbonization device comprises a gas input port and a liquid input port, the gas input device is hermetically connected to the gas input port and communicated with the carbonization device, and the liquid input device is hermetically connected to the liquid input port and communicated with the carbonization device;
the gas input device comprises an ammonia gas input pipeline and a carbon dioxide gas input pipeline, the liquid is a liquid containing calcium ions and/or magnesium ions, the ammonia gas and the carbon dioxide gas input into the gas input device and the liquid containing the calcium ions and/or the magnesium ions input into the liquid input device are subjected to gas-liquid mixing at the upper end inside the carbonization device to form a gas-liquid mixture, and the gas-liquid mixture reacts in the carbonization device to generate carbonate solids, liquid which is not completely reacted and gas which is not completely reacted;
the circulating device is used for circularly conveying at least one of the carbonate solid, the liquid which is not completely reacted and the gas which is not completely reacted to the upper end of the carbonization device again and entering the carbonization device for circular reaction.
2. The system of claim 1, wherein the gas input device further comprises a gas mixing channel, the gas mixing channel is connected between the gas input port of the carbonization device and the ammonia gas input pipeline and the carbon dioxide gas input pipeline, and is used for mixing the ammonia gas output by the ammonia gas input pipeline and the carbon dioxide output by the carbon dioxide gas input pipeline and inputting the mixture into the carbonization device.
3. The system of claim 1, wherein a venturi is disposed in the interior chamber of the carbonator, the venturi being isolated from the interior wall of the carbonator, the venturi comprising an inlet portion disposed proximate the gas and liquid input ports, a narrow portion disposed distal the gas and liquid input ports, and an outlet portion, the narrow portion disposed between the inlet portion and the outlet portion;
the gas-liquid mixture moves to the narrow part and the outlet part from the inlet part in sequence, the gas-liquid mixture reacts in the movement process to generate carbonate solid, liquid which is not completely reacted and gas which is not completely reacted, the carbonate solid and the liquid which is not completely reacted are settled to the lower end of the carbonization device to form a solid-liquid mixture, and the gas which is not completely reacted is discharged from the lower end of the outlet part.
4. The system according to claim 4, wherein the lower end of the carbonization device is provided with a gas outlet which is connected with a gas output pipeline, and the gas output pipeline is communicated with the gas input device so as to input the unreacted gas into the gas input device again for recycling.
5. The system according to claim 4, wherein the bottom of the carbonization device is further provided with a solid-liquid mixture output device, the solid-liquid mixture output device is provided with an output pipeline, the output pipeline is communicated with the upper end of the carbonization device, and the solid-liquid mixture is input into the liquid input port again for recycling.
6. The system of claim 4, wherein the solid-liquid mixture output device comprises a solid-liquid separator connected with the output pipeline, the solid-liquid separator is used for separating the solid-liquid mixture into carbonate solids and liquid without complete reaction, the carbonate solids are output to external equipment, and the liquid without complete reaction is input to the liquid input port again through the output pipeline for recycling.
7. The system of claim 1, wherein the time for the cyclical reaction is greater than 10 min.
8. A method for producing solid carbonate using the system of any one of claims 1-7, the method comprising the steps of:
mixing carbon dioxide gas and ammonia gas to obtain mixed gas, and inputting the mixed gas into a carbonization device;
feeding a liquid comprising calcium ions and/or magnesium ions to a carbonization device;
mixing the mixed gas and the liquid containing calcium ions and/or magnesium ions at the upper part in the inner cavity of the carbonization device to form a gas-liquid mixture, wherein the gas-liquid mixture moves from the upper end to the lower end of the carbonization device;
and the gas-liquid mixture moves to the lower end of the carbonization device to form carbonate solid, liquid which is not completely reacted and gas which is not completely reacted, the carbonate solid and the liquid which is not completely reacted are settled to the lower end of the carbonization device to form a solid-liquid mixture, the liquid which is not completely reacted in the solid-liquid mixture is output from the carbonization device and is input into the carbonization device again from the upper part of the carbonization device through a circulating device, the gas which is not completely reacted is output from the carbonization device, and part of the output gas enters the mixed gas again through the circulating device.
9. The method according to claim 8, characterized in that the molar concentration ratio of the flow rates per second of ammonia gas, carbon dioxide gas and liquid containing calcium ions and/or magnesium ions is: ammonia gas, carbon dioxide gas and liquid containing calcium ions and/or magnesium ions are 1: 10-1000: 2-10, wherein the molar concentration of the liquid containing calcium ions and/or magnesium ions refers to the molar concentration of calcium ions and/or magnesium ions.
10. A carbonate solid produced by the method of claim 8 or 9, wherein the carbonate solid is at least one of magnesium-containing calcium carbonate, or magnesium carbonate.
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