CN103113208A - Continuous production process for preparing calcium formate through calcium hydroxide carbonylation - Google Patents
Continuous production process for preparing calcium formate through calcium hydroxide carbonylation Download PDFInfo
- Publication number
- CN103113208A CN103113208A CN2013100610281A CN201310061028A CN103113208A CN 103113208 A CN103113208 A CN 103113208A CN 2013100610281 A CN2013100610281 A CN 2013100610281A CN 201310061028 A CN201310061028 A CN 201310061028A CN 103113208 A CN103113208 A CN 103113208A
- Authority
- CN
- China
- Prior art keywords
- calcium
- reaction
- calcium hydroxide
- continuous production
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a continuous production process for preparing calcium formate through calcium hydroxide carbonylation. The continuous production process has the beneficial effects that the conversion rate of calcium hydroxide can be more than 99% by adopting the modes of series connection or parallel connection of one or more pressurized reaction kettles and circulation of the unreacted liquid material; reaction accelerants are added to the reaction materials to improve the reaction rate; the calcium formate product is separated from the impurities in the raw materials by adopting a filter method and the product with calcium formate purity more than 99% is finally obtained through evaporative crystallization, separation and drying; the gases obtained by purifying industrial waste gases rich in CO and carbide slag rich in calcium hydroxide can be used as the raw materials; and the method is low in production cost and simple in process, easily achieves large-scale continuous automatic production and has stronger market competitiveness.
Description
Technical field
The present invention relates to a kind of continuous production processes method that is prepared calcium formiate by the calcium hydroxide carbonylation.
Background technology
Calcium formiate is of many uses, can be used for fodder additives, cement early strength agent, Desulphurization of fuels agent, foodstuffs industry additive, plant-growth regulator, petroleum industry probing auxiliary agent, tanning industry auxiliary agent etc.China's calcium formiate market capacity only has 50,000 ton/years at present, is mainly used in fodder additives, foodstuffs industry additive etc.Major cause is that the calcium formiate production cost is high, and price is high, and this has limited the application of calcium formiate at other field.If can developing low-cost calcium formiate synthesis technique, reduce its price, can promote its widespread use in fields such as concrete additive, sweetening agents.With current China concrete year usage quantity approximately 25 billion cubic meters calculate, wherein ready mixed concrete amount is 6 billion cubic meters, needs to use the amount of concrete of hardening accelerator to be about 3000 ten thousand steres, if the addition of calcium formiate, at 1%wt, year needs the hardening accelerator amount to be about 900,000 tons.At present China's desulfurization with Wingdale and unslaked lime year usage quantity be about 1,000 ten thousand tons, if the addition of calcium formiate, at 2%wt, year needs the calcium formiate amount to be about 200,000 tons, the demand that expects the year two thousand twenty China calcium formiate can be over 1,000,000 ton/years.
Existing calcium formate producing process comprises the catalysis method of double decomposition, calcium oxide and formaldehyde reaction of the sand-like calcium formiate of neutralisation resultant current, sodium formiate and nitrocalcite of neutralisation, calcium carbonate and formic acid of calcium oxide and formic acid and polyhydroxy-alcohol by-product calcium formiate method etc.Mainly there is following defect in these methods: (1) raw materials cost is higher, and as formic acid, formaldehyde, sodium formiate etc., (2) should not form large-scale production, as polyhydroxy-alcohol by-product calcium formiate method.Therefore rely on existing production technique that calcium formiate product of high quality and at a reasonable price can't be provided in a large number, meet the demand of future market to calcium formiate.In order to solve the problems such as existing calcium formate producing process cost is high, throughput is lower, propose to use the calcium hydroxide carbonylation to prepare the calcium formiate new technology.Preparing the calcium formiate reaction principle by the calcium hydroxide carbonylation method is shown below:
Solubleness due to calcium hydroxide in water is lower, mainly with solid particulate, exists, and reactant CO is gas, so in reaction process, the mass transfer between gas phase, liquid phase and solid phase is the key factor of this technique.Patent [CN201325936Y] has reported that a kind of carbon monoxide and calcium hydroxide carbonylation prepare the tower reactor of calcium formiate, this device utilizes the mass transfer between rectifying tower structure strengthening liquid phase, intensified response speed, but liquid-solid mass transfer is poor, the reactor design complexity, easily fouling, and the overall craft process of continuous production calcium formiate is not proposed.Patent [CN101880223A] has been reported a kind of method of utilizing carbon monoxide and calcium hydroxide to prepare calcium formiate, makes calcium hydroxide emulsion and carbon monoxide react synthetic calcium formiate reaction solution in tubular reactor, through Crystallization Separation, obtains calcium formiate.Because there is the turning, many places in tubular reactor, can cause the fouling of insolubles deposition and affect the continuity of its mobility and process.In addition, tubular reactor relies on gas phase rapid flow strengthening gas-liquid mass transfer, is difficult to the residence time that reaches longer, and feed stock conversion is relatively low.Given this, the present invention proposes a kind of continuous production processes method that is prepared calcium formiate by the calcium hydroxide carbonylation.
Summary of the invention
An object of the present invention is to provide a kind of continuous production processes of being produced calcium formiate by the calcium hydroxide carbonylation, can be applicable in extensive calcium formiate production.This technique is used the compressive reaction still, uses the pattern of a compressive reaction still or a plurality of compressive reaction still serial or parallel connections, in each compressive reaction still, is provided with stirring rake, baffle plate, gas and liquid feed distributor.Mass transfer between gas-liquid-solid in reaction process by strengthening to be to accelerate speed of reaction, and adopts and add the mode of reaction promotor to improve speed of reaction in reactant, adopts the mode of unreacted material circulation can make the calcium hydroxide transformation efficiency reach more than 99%.Adopt filter method that the calcium formiate product is separated with the impurity in raw material, and finally obtain calcium formiate purity at the product more than 99% by evaporative crystallization, separation, drying.The present invention can utilize carbide slag to replace calcium hydroxide as raw material, is directly used in the production calcium formiate.Production cost is low; Technique is simple, is easy to realize extensive continuous automatic production, has the stronger market competitiveness.Not only can realize the Efficient Cycle utilization of solid waste, also help environment protection, there is huge economic and social benefit.
The step comprised by the continuous production processes of calcium hydroxide carbonylation production calcium formiate provided by the invention:
1) use a compressive reaction still or a plurality of compressive reaction still serial or parallel connections of (for example: two) more than;
2) in each compressive reaction still, stirring rake is set, inwall arranges vertical or sloping baffle, in CO (carbon monoxide converter) gas charging and calcium hydroxide emulsion liquid feeding place, gas distributor and liquid distributor are set respectively, with the mass transfer by between gas-liquid-solid in the strengthening reaction process, improve speed of reaction.
3) by overflow weir, reacted material is flowed out, adopt settlement separate method to make calcium formiate product and the initial gross separation of unreacted hydrogen calcium oxide, unreacted calcium hydroxide material flows out from the bottom of subsider as circulation fluid, is recycled in the compressive reaction still and continues reaction.
4) calcium formate solution after the separation is delivered to the multiple-effect evaporator condensing crystal again after flame filter press filters, then via separating centrifuge separation, drying machine drying.
5) pattern of a plurality of compressive reaction still series connection is that gas phase and the liquid phase material that first compressive reaction still is flowed out enters into respectively second compressive reaction still continuation reaction, the liquid phase material flowed out in last compressive reaction still is delivered in settlement separator, utilize calcium formiate and calcium hydroxide and impurity different solubility in water to make to deliver to follow-up workshop section after the calcium formate solution initial gross separation, unreacted calcium hydroxide and partial impurities is completely delivered in first compressive reaction still and is continued reaction by recycle pump, to guarantee the calcium hydroxide complete reaction.After further removing impurity through flame filter press, the calcium formate solution of extraction settlement separator enters the calcium formiate mother liquor tank, again by being pumped to multiple-effect reduction vaporization crystallizer, crystalline product liquid is delivered to moisture eliminator after centrifuging, and drying obtains the calcium formiate solid particulate.
6) pattern of many stills parallel connection and the difference of connecting are that the gas-phase feed of each compressive reaction still is all that fresh CO (carbon monoxide converter) gas and each compressive reaction still has independently gas phase emission mouth.
Described compressive reaction still inside arranges stirring rake, baffle, flow deflector and overflow groove.
The reaction pressure of described compressive reaction still is generally 1.5 MPa ~ 8 MPa, is preferably 2 MPa ~ 6 MPa;
The service temperature of described compressive reaction still is generally 160 ℃ ~ 230 ℃, is preferably 170 ℃ ~ 200 ℃.
Solid content in described calcium hydroxide emulsion is 50 g/L ~ 300 g/L, is preferably 80 g/L ~ 200 g/L.
Described carbon monoxide feed gas concentration be 50% ~ 100% (
φ), be preferably 80% ~ 100% (
φ), all the other are N
2.
Described calcium hydroxide emulsion and CO feeding temperature are 140 ℃ ~ 200 ℃, are preferably 160 ℃ ~ 180 ℃.
Described drying temperature is 120 ℃ ~ 180 ℃, is preferably 80 ~ 150 ℃.Drying means can be fluidised bed drying or air flow bed drying.
Described circulating fluid flow rate and fresh hydrogen calcium oxide feed liquid flow (L/h), than being generally 0.05 ~ 5, are preferably 0.5 ~ 1.5.The interpolation quality of reaction promotor (one or more in formic acid, formate, oxalic acid, oxalate, sodium hydroxide, potassium hydroxide) and the fresh hydrogen calcium oxide mass ratio of interpolation are 0.001 ~ 0.01, are preferably 0.004 ~ 0.008.
After described reaction, product liquid filter method is Plate Filtration.
Described crystallization method is the multiple-effect evaporation crystal system, adopts the pump circulation crystallizer, and crystallization range is 60 ~ 170 ℃.
Described crystalline product and mother liquor separation method are piston material pushing centrifuging.
When low to the reaction product purity requirement, can not adopt settlement separator, the thick solution of calcium formiate that reaction is generated directly enters follow-up workshop section.
Carbide slag and calcium carbide stove exhaust that the present invention can utilize carbide acetylene method to prepare and produce in the polyvinyl chloride process are the raw material production calcium formiate, realize the recycling of calcium carbide waste slag and waste gas.
The present invention adopts the mode of a compressive reaction still or a plurality of compressive reaction still serial or parallel connection and unreacted liquid Matter Transfer can make the calcium hydroxide transformation efficiency reach more than 99%.Employing adds reaction promotor to improve speed of reaction in reaction mass.Adopt filter method that the calcium formiate product is separated with the impurity in raw material, and finally obtain calcium formiate purity at the product more than 99% by evaporative crystallization, separation, drying.The industrial waste gas purifying gained gas that is rich in CO and the carbide slag that is rich in calcium hydroxide are raw material to adopt the inventive method also can use, and production cost is low, and technique is simple, is easy to realize extensive continuous automatic production, has the stronger market competitiveness.
Adopt calcium formiate constant product quality that the inventive method produces, easy to control, content can reach more than 99%; Feed stock conversion is high, and the calcium hydroxide transformation efficiency can reach more than 99%; The CO source of the gas that raw material can adopt carbide slag and be obtained by industrial gaseous waste, production cost is low; Technique is simple, is easy to realize extensive continuous automatic production, has the stronger market competitiveness.Not only can realize the Efficient Cycle utilization of solid waste, also help environment protection, there is huge economic and social benefit.
The accompanying drawing explanation
The sectional view of Fig. 1 compressive reaction still.
The sectional view of two compressive reaction stills of Fig. 2 parallel connection.
The sectional view of two compressive reaction still series connection of Fig. 3.
Fig. 4 equipment connection and schematic flow sheet.
Embodiment
Be further explained in detail the present invention by the description below with reference to embodiment, but below comprise that the description of embodiment, only for making those skilled in the art in the invention can more be expressly understood principle of the present invention, does not mean that the present invention is carried out to any type of restriction.The equipment used in the present invention and reagent are the commercially available universal product in case of no particular description.
Provided by the inventionly a kind ofly by the calcium hydroxide carbonylation, prepare the step that the continuous production processes of calcium formiate comprises: calcium hydroxide emulsion and carbon monoxide react synthetic calcium formate solution in the compressive reaction still of one or more serial or parallel connections, after filtration, obtain the calcium formiate product after crystallization, separation, drying.
This technique is used the compressive reaction still, can use the pattern of a compressive reaction still or a plurality of compressive reaction still serial or parallel connections, in each compressive reaction still, stirring rake is set, inwall arranges vertical or sloping baffle, at gas feed and liquid feeding place, gas distributor and liquid distributor are set respectively, with the mass transfer by between gas-liquid-solid in the strengthening reaction process, improve speed of reaction.By overflow weir, reacted material is flowed out, adopt settlement separate method to make calcium formiate product and the initial gross separation of unreacted hydrogen calcium oxide, unreacted material flows out from the bottom of subsider, is recycled in the compressive reaction still and continues reaction, and the calcium hydroxide transformation efficiency is reached more than 99%.Calcium formate solution after separation is delivered to the multiple-effect evaporator condensing crystal again after flame filter press filters, then via after separating centrifuge separation, drying machine drying, obtaining calcium formiate purity at the product more than 99%.
The present invention can adopt the pattern of a compressive reaction still or a plurality of compressive reaction still serial or parallel connections.The volume of still is 1000 L.The pattern of many still series connection is that gas phase and liquid phase material that first compressive reaction still is flowed out enter into respectively second compressive reaction still continuation reaction, the liquid phase material flowed out in last compressive reaction still is delivered in settlement separator, utilize calcium formiate and calcium hydroxide and impurity different solubility in water to make to deliver to follow-up workshop section after the calcium formate solution initial gross separation, unreacted calcium hydroxide and partial impurities is completely delivered in first compressive reaction still and is continued reaction by recycle pump, to guarantee the calcium hydroxide complete reaction.After further removing impurity through flame filter press, the calcium formate solution of extraction settlement separator enters the calcium formiate mother liquor tank, again by being pumped to multiple-effect reduction vaporization crystallizer, crystalline product liquid is delivered to moisture eliminator after centrifuging, obtain the calcium formiate solid particulate 120 ℃ ~ 180 ℃ dryings, calcium formiate content can reach more than 99%.The pattern of many stills parallel connection and the difference of connecting are that the gas-phase feed of each compressive reaction still is all that fresh CO (carbon monoxide converter) gas and each reactor has independently gas phase emission mouth.
As Fig. 1 ~ Fig. 4, the various piece numeral of flow process in figure, the same function of identical numeral.Each digitized representation meaning is as follows: 1: the raw pulp machine; The 2:CO compressor; 3: fluid delivery pump; 4: the compressive reaction still; 5: agitator; 6: settlement separator; 7: flame filter press; 8: mother liquor tank; 9: Multi-effect evaporation crystallizer; 10: centrifugal filter; 11: drying machine; 12: wrapping machine; 13: traverse baffle; 14: liquid distributor; 15: overflow groove; 16: flow deflector; 17: gas distributor.
The single compressive reaction still of embodiment 1 is investigated result
Adopt single compressive reaction still, adopt the two-stage stirring rake in still, CO gas producer gas generator generated in conjunction with Fig. 4 is sloughed H through refining plant
2s, CO
2deng impurity, and after Pressure Swing Adsorption to CO volume content is 99%, the compressed machine 2 of CO gas is forced into to 2.5 MPa, the another calcium hydroxide emulsion that is 80 g/L by concentration is forced into 2.5 MPa through fluid delivery pump 3-1, two kinds of materials are preheated to 160 ℃ with flow 2400 L (mark condition)/h and 80 L/h through preheater respectively and enter compressive reaction still 4-1, in the compressive reaction still, temperature control is 170 ℃, pressure 2 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.004, mixing speed is 60 rpm, reaction with this understanding, reaction solution autoreaction still top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 0.5.Calcium formiate content 99.5% in finished product, calcium hydroxide transformation efficiency 99.3%.
The single compressive reaction still of embodiment 2 is investigated result
Adopt single compressive reaction still, adopt the two-stage stirring rake in still, in conjunction with Fig. 4, will slough H through refining plant from the rich CO gas of yellow phosphoric tail gas
2s, CO
2deng impurity, after Pressure Swing Adsorption to CO volume content is 99%, the compressed machine 2 of CO gas is forced into to 2.5 MPa, the carbide slag emulsion that will be separately 200 g/L containing calcium hydroxide concentration is forced into 2.5 MPa through pump 3-1, two kinds of materials are preheated to 160 ℃ with flow 2400 L (mark condition)/h and 35 L/h through preheater respectively and enter compressive reaction still 4-1, in the compressive reaction still, temperature control is 170 ℃, pressure 2 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.008, mixing speed is 60 rpm, reaction with this understanding, reaction solution autoreaction still top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 0.8.The calcium hydroxide transformation efficiency is more than 99.3%, calcium formiate content 99.5% in product.
The single compressive reaction still of embodiment 3 is investigated result
Adopt single compressive reaction still, adopt the two-stage stirring rake in still, in conjunction with Fig. 4, will slough H through refining plant from the rich CO gas of yellow phosphoric tail gas
2s, CO
2deng impurity, after Pressure Swing Adsorption to CO volume content is 99%, the compressed machine 2 of CO gas is forced into to 6.5 MPa, the another calcium hydroxide emulsion that is 200 g/L by concentration is forced into 6.5 MPa through pump 3-1, two kinds of materials are heated to 180 ℃ with flow 24000 L (mark condition)/h and 300 L/h through preheater respectively and enter compressive reaction still 4-1, in the compressive reaction still, temperature control is 200 ℃, pressure 6 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.008, mixing speed is 60 rpm, reaction with this understanding, reaction solution autoreaction still top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 0.8.The calcium hydroxide transformation efficiency is more than 99.3%, calcium formiate content 99.5% in product.
Result is investigated in 4 two compressive reaction still series connection of embodiment
Adopt two compressive reaction still series connection, CO gas producer gas generator generated in conjunction with Fig. 4 is sloughed H through refining plant
2s, CO
2deng impurity, after Pressure Swing Adsorption to CO volume content is 80%, the compressed machine 2 of CO gas is forced into to 6.5 MPa, the another calcium hydroxide emulsion that is 200 g/L by concentration is forced into 6.5 MPa through pump 3-1, two kinds of materials are preheated to 180 ℃ with flow 66000 L (mark condition)/h and 1000 L/h through preheater respectively and enter in series pressurized reactor 4-1, as shown in Fig. 3 mode of connection, in two compressive reaction stills, temperature control is 200 ℃, pressure 6 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.008, mixing speed is 60 rpm, reaction with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 1.2.Calcium hydroxide transformation efficiency 100%, calcium formiate content 99.5% in product.
5 two compressive reaction stills of embodiment result of investigating in parallel
Adopt the parallel connection of two compressive reaction stills, adopt the two-stage stirring rake in still, in conjunction with Fig. 4, will slough H through refining plant from the rich CO gas of yellow phosphoric tail gas
2s, CO
2after impurity, the CO gas that to obtain the CO volume content be 80%, compressed machine 2 is forced into 6.5 MPa again, the another calcium hydroxide emulsion that is 200 g/L by concentration is forced into 6.5 MPa through pump 3-1, two kinds of materials are preheated to 180 ℃ with flow 72000 L (mark condition)/h and 1200 L/h through preheater respectively and enter in compressive reaction still 4-1 in parallel, as shown in Fig. 2 mode of connection, in two compressive reaction stills, temperature control is 200 ℃, pressure 6 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.004, mixing speed is 60 rpm, reaction with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 1.4.Calcium hydroxide transformation efficiency 100%, calcium formiate content 99.5% in product.
Result is investigated in 6 two compressive reaction still series connection of embodiment
Adopt two compressive reaction still series connection, adopt the two-stage stirring rake in still, CO gas producer gas generator generated in conjunction with Fig. 4 is sloughed H through refining plant
2s, CO
2after impurity, after Pressure Swing Adsorption to CO volume content is 80%, compressed machine 2 is forced into 2.5 MPa again, the another calcium hydroxide emulsion that is 80 g/L by concentration is forced into 2.5 MPa through pump 3-1, two kinds of materials are preheated to 160 ℃ with flow 6600 L (mark condition)/h and 150 L/h through preheater respectively and enter compressive reaction still 4-1, in compressive reaction still 4-1, as shown in Fig. 2 mode of connection, in two compressive reaction stills, temperature control is 170 ℃, pressure 2 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.004, mixing speed is 60 rpm, reaction with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 0.6.Calcium hydroxide transformation efficiency 99.5%, calcium formiate content 99.5% in product.
7 two compressive reaction stills of embodiment result of investigating in parallel
Adopt the parallel connection of two compressive reaction stills, adopt the two-stage stirring rake in still, CO gas producer gas generator generated in conjunction with Fig. 4 is sloughed H through refining plant
2s, CO
2after impurity, after Pressure Swing Adsorption to CO volume content is 80%, compressed machine 2 is forced into 2.5 MPa again, the another calcium hydroxide emulsion that is 80 g/L by concentration is forced into 2.5 MPa through pump 3-1, two kinds of materials are preheated to 160 ℃ with flow 7200 L (mark condition)/h and 180 L/h through preheater respectively and enter compressive reaction still 4-1, as shown in Fig. 2 mode of connection, in two compressive reaction stills, temperature control is 170 ℃, pressure 2 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.004, mixing speed is 60 rpm, reaction with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 0.6.The calcium hydroxide transformation efficiency is more than 99%, calcium formiate content in product > 99.5%.
8 two compressive reaction stills of embodiment result of investigating in parallel
Adopt the parallel connection of two compressive reaction stills, adopt the two-stage stirring rake in still, CO gas producer gas generator generated in conjunction with Fig. 4 is sloughed H through refining plant
2s, CO
2after impurity, after Pressure Swing Adsorption to CO volume content is 99%, compressed machine 2 is forced into 6.5 MPa again, the carbide slag emulsion that will be separately 200 g/L containing calcium hydroxide concentration is forced into 6.5 MPa through pump 3-1, two kinds of materials are preheated to 180 ℃ with flow 72000 L (mark condition)/h and 1300 L/h through preheater respectively and enter compressive reaction still 4-1, as shown in Fig. 2 mode of connection, in two compressive reaction stills, temperature control is 200 ℃, pressure 6 MPa, the interpolation quality of reaction promotor (formic acid) and fresh hydrogen calcium oxide mass ratio are 0.004, mixing speed is 60 rpm, reaction with this understanding, end reaction liquid self-pressurization reactor 4-2 top overflows and enters settlement separator 6, obtain the calcium formiate mother liquor after flame filter press 7, this mother liquor is isolated calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 ℃ of dry finished product calcium formiates that obtain.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, turns back to compressive reaction still 4-1 through recycle pump 3-2 and continues reaction, and internal circulating load and fresh hydrogen calcium oxide feed liquid throughput ratio are 1.5.The calcium hydroxide transformation efficiency is more than 99%, calcium formiate content in product > 99.5%.
Claims (10)
1. a continuous production processes of being produced calcium formiate by the calcium hydroxide carbonylation is characterized in that the step comprised:
1) use a compressive reaction still or more than one a plurality of compressive reaction still serial or parallel connection;
2) in each compressive reaction still, stirring rake is set, inwall arranges vertical or sloping baffle, in CO (carbon monoxide converter) gas charging and calcium hydroxide emulsion liquid feeding place, gas distributor and liquid distributor are set respectively, with the mass transfer by between gas-liquid-solid in the strengthening reaction process, improve speed of reaction;
3) by overflow weir, reacted material is flowed out, adopt settlement separate method to make calcium formiate product and the initial gross separation of unreacted hydrogen calcium oxide, unreacted calcium hydroxide material flows out from the bottom of subsider as circulation fluid, is recycled in the compressive reaction still and continues reaction;
4) calcium formate solution after the separation is delivered to the multiple-effect evaporator condensing crystal again after flame filter press filters, then via separating centrifuge separation, drying machine drying;
5) pattern of a plurality of compressive reaction still series connection is that gas phase and the liquid phase material that first reactor is flowed out enters into respectively second reactor continuation reaction, the liquid phase material flowed out in last reactor is delivered in settlement separator, utilize calcium formiate and calcium hydroxide and impurity different solubility in water to make to deliver to follow-up workshop section after the calcium formate solution initial gross separation, unreacted calcium hydroxide and partial impurities is completely delivered in first reactor and is continued reaction by recycle pump, to guarantee the calcium hydroxide complete reaction, after further removing impurity through flame filter press, the calcium formate solution of extraction settlement separator enters the calcium formiate mother liquor tank, again by being pumped to multiple-effect reduction vaporization crystallizer, crystalline product liquid is delivered to moisture eliminator after centrifuging, drying obtains the calcium formiate solid particulate, when low to the reaction product purity requirement, do not adopt settlement separator, the thick solution of calcium formiate that reaction is generated directly enters follow-up workshop section,
6) pattern of a plurality of autoclave parallel connections and the difference of connecting are that the gas-phase feed of each reactor is all that fresh CO (carbon monoxide converter) gas and each reactor has independently gas phase emission mouth.
2. continuous production processes according to claim 1, is characterized in that described compressive reaction still inside is provided with two-stage stirring rake, baffle, flow deflector and overflow groove.
3. continuous production processes according to claim 1, the reaction pressure that it is characterized in that described compressive reaction still is 1.5 MPa ~ 8 MPa.
4. continuous production processes according to claim 1, the service temperature that it is characterized in that described compressive reaction still is 160 ℃ ~ 230 ℃.
5. continuous production processes according to claim 1, is characterized in that the solid content in described calcium hydroxide emulsion is 50 g/L ~ 300 g/L.
6. continuous production processes according to claim 1, it is characterized in that described carbon monoxide feed gas concentration be 50% ~ 100% (
φ).
7. continuous production processes according to claim 1, is characterized in that described calcium hydroxide and CO feeding temperature are 140 ℃ ~ 200 ℃.
8. continuous production processes according to claim 1, the temperature that it is characterized in that described moisture eliminator is 120 ℃ ~ 180 ℃.
9. continuous production processes according to claim 1, is characterized in that described circulating fluid flow rate and fresh hydrogen calcium oxide feed liquid flow (L/h) are than being generally 0.05 ~ 5.
10. continuous production processes according to claim 1, it is characterized in that reaction promotor is one or more in formic acid, formate, oxalic acid, oxalate, sodium hydroxide, potassium hydroxide, adding quality and fresh hydrogen calcium oxide mass ratio is 0.001 ~ 0.01.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310061028.1A CN103113208B (en) | 2013-02-27 | 2013-02-27 | The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310061028.1A CN103113208B (en) | 2013-02-27 | 2013-02-27 | The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103113208A true CN103113208A (en) | 2013-05-22 |
| CN103113208B CN103113208B (en) | 2015-08-26 |
Family
ID=48411624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310061028.1A Active CN103113208B (en) | 2013-02-27 | 2013-02-27 | The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103113208B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274921A (en) * | 2013-05-24 | 2013-09-04 | 湖北吉星化工集团有限责任公司 | Device and method for preparing calcium formate by utilizing yellow phosphorus tail gas |
| CN103601630A (en) * | 2013-07-08 | 2014-02-26 | 曹正祥 | Method utilizing calcium carbide slag and carbon monoxide to synthesize calcium formate |
| CN103664571A (en) * | 2013-12-25 | 2014-03-26 | 云南省化工研究院 | Method for synthesizing calcium formate by using industrial emission carbon monoxide exhaust gas through batch reaction |
| CN103804175A (en) * | 2013-12-25 | 2014-05-21 | 云南省化工研究院 | Method for synthesizing calcium formate with coproduction of potassium formate from industrial emission carbon monoxide tail gas |
| CN104387255A (en) * | 2014-11-11 | 2015-03-04 | 湖北瑞富阳化工科技有限公司 | Preparation method of calcium formate |
| CN106748727A (en) * | 2016-11-09 | 2017-05-31 | 西南化工研究设计院有限公司 | A kind of method of calcium hydroxide carbonylation production calcium formate |
| CN109320411A (en) * | 2018-11-22 | 2019-02-12 | 湖南湘硕化工有限公司 | A kind of preparation method of calcium formate |
| CN109422641A (en) * | 2017-09-05 | 2019-03-05 | 天津大学 | The continuous producing method of calcium formate is prepared by yellow phosphoric tail gas |
| CN109879747A (en) * | 2019-04-01 | 2019-06-14 | 辽宁赛菲化学有限公司 | A kind of method of carbide slag production calcium formate |
| CN113548956A (en) * | 2021-07-30 | 2021-10-26 | 四川信乙化工有限公司 | Continuous production system of phenylacetic acid |
| CN114082216A (en) * | 2021-11-24 | 2022-02-25 | 赤峰瑞阳化工有限公司 | Efficient evaporation crystallization method of calcium formate |
| CN116143179A (en) * | 2022-09-09 | 2023-05-23 | 河北圣雪大成制药有限责任公司 | Method for preparing ferrous sulfate for Fenton oxidation by using oxytetracycline hydrochloride waste acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273962A (en) * | 2000-03-31 | 2000-11-22 | 杨显云 | Process for synthesizing potassium formate |
| CN102580629A (en) * | 2012-03-20 | 2012-07-18 | 中国天辰工程有限公司 | Gas-liquid-liquid-solid reaction device |
-
2013
- 2013-02-27 CN CN201310061028.1A patent/CN103113208B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273962A (en) * | 2000-03-31 | 2000-11-22 | 杨显云 | Process for synthesizing potassium formate |
| CN102580629A (en) * | 2012-03-20 | 2012-07-18 | 中国天辰工程有限公司 | Gas-liquid-liquid-solid reaction device |
Non-Patent Citations (1)
| Title |
|---|
| 武红杰,: "氢氧化钙羰基化合成甲酸钙工艺研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274921B (en) * | 2013-05-24 | 2014-06-25 | 湖北吉星化工集团有限责任公司 | Device and method for preparing calcium formate by utilizing yellow phosphorus tail gas |
| CN103274921A (en) * | 2013-05-24 | 2013-09-04 | 湖北吉星化工集团有限责任公司 | Device and method for preparing calcium formate by utilizing yellow phosphorus tail gas |
| CN103601630A (en) * | 2013-07-08 | 2014-02-26 | 曹正祥 | Method utilizing calcium carbide slag and carbon monoxide to synthesize calcium formate |
| CN103664571B (en) * | 2013-12-25 | 2016-03-09 | 云南省化工研究院 | A kind of method of industrial discharge carbon monoxide tail gas intermittent reaction synthesis calcium formiate |
| CN103664571A (en) * | 2013-12-25 | 2014-03-26 | 云南省化工研究院 | Method for synthesizing calcium formate by using industrial emission carbon monoxide exhaust gas through batch reaction |
| CN103804175A (en) * | 2013-12-25 | 2014-05-21 | 云南省化工研究院 | Method for synthesizing calcium formate with coproduction of potassium formate from industrial emission carbon monoxide tail gas |
| CN103804175B (en) * | 2013-12-25 | 2016-03-09 | 云南省化工研究院 | A kind of method of industrial discharge carbon monoxide tail gas synthesis calcium formiate co-producing potassium formate |
| CN104387255B (en) * | 2014-11-11 | 2017-01-25 | 湖北瑞富阳化工科技有限公司 | Preparation method of calcium formate |
| CN104387255A (en) * | 2014-11-11 | 2015-03-04 | 湖北瑞富阳化工科技有限公司 | Preparation method of calcium formate |
| CN106748727A (en) * | 2016-11-09 | 2017-05-31 | 西南化工研究设计院有限公司 | A kind of method of calcium hydroxide carbonylation production calcium formate |
| CN106748727B (en) * | 2016-11-09 | 2019-06-28 | 西南化工研究设计院有限公司 | A kind of method of calcium hydroxide carbonylation production calcium formate |
| CN109422641A (en) * | 2017-09-05 | 2019-03-05 | 天津大学 | The continuous producing method of calcium formate is prepared by yellow phosphoric tail gas |
| CN109320411A (en) * | 2018-11-22 | 2019-02-12 | 湖南湘硕化工有限公司 | A kind of preparation method of calcium formate |
| CN109879747A (en) * | 2019-04-01 | 2019-06-14 | 辽宁赛菲化学有限公司 | A kind of method of carbide slag production calcium formate |
| CN113548956A (en) * | 2021-07-30 | 2021-10-26 | 四川信乙化工有限公司 | Continuous production system of phenylacetic acid |
| CN114082216A (en) * | 2021-11-24 | 2022-02-25 | 赤峰瑞阳化工有限公司 | Efficient evaporation crystallization method of calcium formate |
| CN116143179A (en) * | 2022-09-09 | 2023-05-23 | 河北圣雪大成制药有限责任公司 | Method for preparing ferrous sulfate for Fenton oxidation by using oxytetracycline hydrochloride waste acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103113208B (en) | 2015-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113208B (en) | The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation | |
| CN106631684A (en) | Method for preparing SBA(sec-butyl alcohol) through hydrolysis with sec-butyl acetate | |
| CN107522602B (en) | Process and system for preparing DMM2 | |
| CN104478644B (en) | A kind of tert-butyl alcohol is prepared the method for isobutene | |
| CN110877914A (en) | Method for preparing high-purity high-white calcium carbonate by mineralizing and fixing carbon dioxide with phosphogypsum | |
| CN105461515A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN101475463B (en) | Method for coproduction of high purity aminic acid and acid sodium phosphate by reaction of calcium formate and peroxyphosphoric acid | |
| CN104119225A (en) | New technology for producing ethyl acetate through reactive distillation by taking mixed ionic liquid as catalyst | |
| CN109422641B (en) | Continuous production method for preparing calcium formate from yellow phosphorus tail gas | |
| CN102964248B (en) | Method for producing nitric oxide and synthesizing dimethyl oxalate through carbonylation | |
| CN106608832B (en) | The process of liquid ammonia process for caustic soda purification and Ammonia Process co-producing ethanol amine | |
| CN1088181A (en) | Tower wet method strong phosphoric acid production method and equipment | |
| CN111153823B (en) | Method for preparing oxamide from dimethyl oxalate | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| CN114644549A (en) | Production system and production process of formic acid | |
| CN114853614A (en) | Triethylamine water removal device and water removal process | |
| CN209810143U (en) | Low boiling point alcohol continuous esterification reaction rectification system | |
| CN210078876U (en) | A partition wall reaction rectifier unit for gathering methoxy dimethyl ether is synthetic | |
| CN100363327C (en) | Production of pivalic acid | |
| CN106517132A (en) | Device and method for recycling phosphorus and magnesium from phosphorus ore magnesium removal liquid | |
| CN111362819A (en) | Process and device for producing glycine by alcohol phase method | |
| CN113248389A (en) | Production system and method of 1, 2-cyclohexanediamine | |
| CN101747177A (en) | Device and method for preparing butane diacid by continuously hydrolyzing dialkyl succinate ester | |
| CN111087319A (en) | Method for continuously preparing glycine in alcohol phase | |
| CN110818565A (en) | Device and process for preparing dimethyl carbonate by ester exchange method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |