CN103113208B - The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation - Google Patents
The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation Download PDFInfo
- Publication number
- CN103113208B CN103113208B CN201310061028.1A CN201310061028A CN103113208B CN 103113208 B CN103113208 B CN 103113208B CN 201310061028 A CN201310061028 A CN 201310061028A CN 103113208 B CN103113208 B CN 103113208B
- Authority
- CN
- China
- Prior art keywords
- calcium
- reaction
- calcium hydroxide
- formiate
- continuous production
- 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.)
- Active
Links
Abstract
The present invention relates to a kind of continuous production processes method being prepared calcium formiate by calcium hydroxide carbonylation.Adopt the mode of a compressive reaction still or multiple compressive reaction still serial or parallel connection and unreacted liquid Matter Transfer that calcium hydroxide transformation efficiency can be made to reach more than 99%.Adopt in reaction mass, add reaction promotor raising speed of reaction.Adopt filter method by the magazins' layout in calcium formiate product and raw material, and finally obtain the product of calcium formiate purity more than 99% by evaporative crystallization, separation, drying.Adopt the inventive method also can use the industrial waste gas purifying gained gas that is rich in CO and be rich in the carbide slag of calcium hydroxide for raw material, production cost is low, and technique is simple, is easy to realize extensive continuous automatic production, has the stronger market competitiveness.
Description
Technical field
The present invention relates to a kind of continuous production processes method being prepared calcium formiate by 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.Current China calcium formiate market capacity only has 50,000 tons/year, is mainly used in fodder additives, foodstuffs industry additive etc.Major cause is that calcium formiate production cost is high, and price is high, which has limited the application of calcium formiate at other field.If can developing low-cost calcium formiate synthesis technique, reduce its price, then can promote its widespread use in the field such as concrete additive, sweetening agent.Calculate with current China concrete year usage quantity about 25 billion cubic meter, wherein ready mixed concrete amount is 6 billion cubic meters, and the amount of concrete of hardening accelerator need be used to be about 3000 ten thousand steres, if the addition of calcium formiate is at 1%wt, then needs hardening accelerator amount to be about 900,000 tons in year.Current China desulfurization Wingdale and unslaked lime year usage quantity be about 1,000 ten thousand tons, if the addition of calcium formiate is at 2%wt, then need calcium formiate amount to be about 200,000 tons in year, the demand expecting the year two thousand twenty China calcium formiate can more than 1,000,000 tons/year.
Existing calcium formate producing process comprises the catalysis method and polyhydroxy-alcohol by-product calcium formiate method etc. of the double decomposition of the sand-like calcium formiate of neutralisation resultant current of the neutralisation of calcium oxide and formic acid, calcium carbonate and formic acid, sodium formiate and nitrocalcite, calcium oxide and formaldehyde reaction.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 cannot provide the calcium formiate product of super quality and competitive price 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 calcium hydroxide carbonylation to prepare calcium formiate new technology.Prepare calcium formiate reaction principle by calcium hydroxide carbonylation method to be shown below:
Because the solubleness of calcium hydroxide in water is lower, mainly exist with solid particulate, reactant CO is gas, and therefore gas phase in reaction process, mass transfer between liquid phase and solid phase are the key factors of this technique.Patent [CN201325936Y] reports the tower reactor that a kind of carbon monoxide and calcium hydroxide carbonylation prepare 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, reactor design is complicated, easy fouling, and the overall craft process not proposing continuous production calcium formiate.Patent [CN101880223A] reports a kind of method utilizing carbon monoxide and calcium hydroxide to prepare calcium formiate, makes calcium hydroxide emulsion and carbon monoxide Reactive Synthesis calcium formiate reaction solution in tubular reactor, obtains calcium formiate through Crystallization Separation.Because tubular reactor exists turning, many places, insolubles can be caused to deposit fouling and affect the continuity of its mobility and process.In addition, tubular reactor relies on gas phase to flow fast strengthening gas-liquid mass transfer, and be difficult to reach the longer residence time, feed stock conversion is relatively low.Given this, the present invention proposes a kind of continuous production processes method being prepared calcium formiate by 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 calcium hydroxide carbonylation, can be applicable in the production of extensive calcium formiate.This technique uses compressive reaction still, uses the pattern of a compressive reaction still or multiple compressive reaction still serial or parallel connection, in each compressive reaction still, is provided with stirring rake, baffle plate, gas and liquid feed distributor.By the mass transfer between gas-liquid-solid in strengthening reaction process to accelerate speed of reaction, and adopt the mode adding reaction promotor in reactant to improve speed of reaction, the mode of employing unreacted Matter Transfer can make calcium hydroxide transformation efficiency reach more than 99%.Adopt filter method by the magazins' layout in calcium formiate product and raw material, and finally obtain the product of calcium formiate purity 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 production calcium formiate.Production cost is low; Technique is simple, is easy to realize extensive continuous automatic production, has the stronger market competitiveness.The Efficient Cycle that not only can realize solid waste utilizes, and also helps environment protection, has huge economic and social benefit.
The step that continuous production processes of producing calcium formiate by calcium hydroxide carbonylation provided by the invention comprises:
1) multiple compressive reaction still serial or parallel connections of a compressive reaction still or more than (such as: two) are used;
2) stirring rake is set in each compressive reaction still, 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 by strengthening reaction process in gas-liquid-solid between mass transfer improve speed of reaction.
3) by overflow weir, reacted material is flowed out, settlement separate method is adopted to make calcium formiate product and the initial gross separation of unreacted hydrogen calcium oxide, unreacted calcium hydroxide material flows out as the bottom of circulation fluid from subsider, is recycled in compressive reaction still and continues reaction.
4) calcium formate solution after being separated delivers to multiple-effect evaporator condensing crystal again after flame filter press filters, then via separating centrifuge separation, drying machine drying.
5) pattern of multiple compressive reaction still series connection the gas phase of first compressive reaction still outflow and liquid phase material is entered into second compressive reaction still respectively continue reaction, the liquid phase material flowed out in last compressive reaction still is delivered in settlement separator, follow-up workshop section is delivered to after utilizing calcium formiate and calcium hydroxide and impurity different solubility in water to make calcium formate solution initial gross separation, unreacted completely calcium hydroxide and partial impurities delivers to continuation reaction in first compressive reaction still, to guarantee calcium hydroxide complete reaction by recycle pump.The calcium formate solution of extraction from settlement separator enters calcium formiate mother liquor tank after impurity removes by flame filter press further, again by being pumped to multiple-effect reduction vaporization crystallizer, crystalline product liquid delivers to moisture eliminator after centrifuging, and drying obtains calcium formiate solid particulate.
6) pattern and the difference of connecting of the parallel connection of many stills are that the gas-phase feed of each compressive reaction still is all 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 DEG C ~ 230 DEG C, is preferably 170 DEG C ~ 200 DEG C.
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 DEG C ~ 200 DEG C, are preferably 160 DEG C ~ 180 DEG C.
Described drying temperature is 120 DEG C ~ 180 DEG C, is preferably 80 ~ 150 DEG C.Drying means can be that fluidised bed drying or air flow bed are dry.
Described circulating fluid flow rate and fresh hydrooxidation calcium feed liquid flow (L/h), than being generally 0.05 ~ 5, are preferably 0.5 ~ 1.5.The interpolation quality of reaction promotor (in formic acid, formate, oxalic acid, oxalate, sodium hydroxide, potassium hydroxide one or more) and the fresh hydrooxidation calcium 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 multiple-effect evaporation crystal system, and adopt pump circulation crystallizer, crystallization range is 60 ~ 170 DEG C.
Described crystalline product and mother liquor separation method are piston material pushing centrifuging.
When lower to reaction product purity requirement, can not settlement separator be adopted, the thick solution of calcium formiate that reaction generates directly is entered follow-up workshop section.
The carbide slag that the present invention can utilize carbide acetylene method to prepare to produce in polyvinyl chloride process and calcium carbide stove exhaust are 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 multiple compressive reaction still serial or parallel connection and unreacted liquid Matter Transfer that calcium hydroxide transformation efficiency can be made to reach more than 99%.Adopt in reaction mass, add reaction promotor raising speed of reaction.Adopt filter method by the magazins' layout in calcium formiate product and raw material, and finally obtain the product of calcium formiate purity more than 99% by evaporative crystallization, separation, drying.Adopt the inventive method also can use the industrial waste gas purifying gained gas that is rich in CO and be rich in the carbide slag of calcium hydroxide for raw material, production cost is low, and technique is simple, is easy to realize extensive continuous automatic production, has the stronger market competitiveness.
The calcium formiate constant product quality adopting the inventive method to produce, easy to control, content can reach more than 99%; Feed stock conversion is high, and 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.The Efficient Cycle that not only can realize solid waste utilizes, and also helps environment protection, has huge economic and social benefit.
Accompanying drawing explanation
The sectional view of Fig. 1 compressive reaction still.
The sectional view of Fig. 2 two compressive reaction stills parallel connection.
The sectional view of Fig. 3 two compressive reaction still series connection.
Fig. 4 equipment connection and schematic flow sheet.
Embodiment
The present invention is further explained in detail by the description below with reference to embodiment, but the description below comprising embodiment, only for enabling those skilled in the art in the invention clearly understand principle of the present invention, not meaning that and carrying out any type of restriction to the present invention.The equipment used in the present invention and reagent are the commercially available universal product in case of no particular description.
The step that a kind of continuous production processes preparing calcium formiate by calcium hydroxide carbonylation provided by the invention comprises: calcium hydroxide emulsion and carbon monoxide Reactive Synthesis calcium formate solution in the compressive reaction still of one or more serial or parallel connection, after filtration, crystallization, separation, obtains calcium formiate product after drying.
This technique uses compressive reaction still, the pattern of a compressive reaction still or multiple compressive reaction still serial or parallel connection can be used, 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 by strengthening reaction process in gas-liquid-solid between mass transfer improve speed of reaction.By overflow weir, reacted material is flowed out, settlement separate method is adopted 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 compressive reaction still and continues reaction, make calcium hydroxide transformation efficiency reach more than 99%.Calcium formate solution after separation delivers to multiple-effect evaporator condensing crystal again after flame filter press filters, then obtains the product of calcium formiate purity more than 99% via after separating centrifuge separation, drying machine drying.
The present invention can adopt the pattern of a compressive reaction still or multiple compressive reaction still serial or parallel connection.The volume of still is 1000 L.The pattern of multi-floating bodies the gas phase of first compressive reaction still outflow and liquid phase material is entered into second compressive reaction still respectively continue reaction, the liquid phase material flowed out in last compressive reaction still is delivered in settlement separator, follow-up workshop section is delivered to after utilizing calcium formiate and calcium hydroxide and impurity different solubility in water to make calcium formate solution initial gross separation, unreacted completely calcium hydroxide and partial impurities delivers to continuation reaction in first compressive reaction still, to guarantee calcium hydroxide complete reaction by recycle pump.The calcium formate solution of extraction from settlement separator enters calcium formiate mother liquor tank after impurity removes by flame filter press further, again by being pumped to multiple-effect reduction vaporization crystallizer, crystalline product liquid delivers to moisture eliminator after centrifuging, obtain calcium formiate solid particulate 120 DEG C ~ 180 DEG C dryings, calcium formiate content can reach more than 99%.Pattern and the difference of connecting of the parallel connection of many stills are that the gas-phase feed of each compressive reaction still is all fresh CO (carbon monoxide converter) gas and each reactor has independently gas phase emission mouth.
As the various piece numeral of flow process in Fig. 1 ~ Fig. 4, figure, the same function of identical numeral.Each digitized representation meaning is as follows: 1: raw pulp machine; 2:CO compressor; 3: fluid delivery pump; 4: 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.
Result investigated by the single compressive reaction still of embodiment 1
Adopt single compressive reaction still, adopt two-stage stirring rake in still, the CO gas that producer gas generator generates is sloughed H through refining plant by composition graphs 4
2s, CO
2deng impurity, and be after 99% through Pressure Swing Adsorption to CO volume content, CO gas is forced into 2.5 MPa through compressor 2, another is that the calcium hydroxide emulsion of 80 g/L is forced into 2.5 MPa through fluid delivery pump 3-1 by concentration, two kinds of materials enter compressive reaction still 4-1 with flow 2400 L (mark condition)/h and 80 L/h through preheater preheats to 160 DEG C respectively, temperature control 170 DEG C in compressive reaction still, pressure 2 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.004, mixing speed is 60 rpm, react with this understanding, reaction solution autoreaction still top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 0.5.Calcium formiate content 99.5% in finished product, calcium hydroxide transformation efficiency 99.3%.
Result investigated by the single compressive reaction still of embodiment 2
Adopt single compressive reaction still, adopt two-stage stirring rake in still, the rich CO gas from yellow phosphoric tail gas is sloughed H through refining plant by composition graphs 4
2s, CO
2deng impurity, be after 99% through Pressure Swing Adsorption to CO volume content, CO gas is forced into 2.5 MPa through compressor 2, separately the carbide slag emulsion containing calcium hydroxide concentration being 200 g/L is forced into 2.5 MPa through pump 3-1, two kinds of materials enter compressive reaction still 4-1 with flow 2400 L (mark condition)/h and 35 L/h through preheater preheats to 160 DEG C respectively, temperature control 170 DEG C in compressive reaction still, pressure 2 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.008, mixing speed is 60 rpm, react with this understanding, reaction solution autoreaction still top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 0.8.Calcium hydroxide transformation efficiency more than 99.3%, calcium formiate content 99.5% in product.
Result investigated by the single compressive reaction still of embodiment 3
Adopt single compressive reaction still, adopt two-stage stirring rake in still, the rich CO gas from yellow phosphoric tail gas is sloughed H through refining plant by composition graphs 4
2s, CO
2deng impurity, be after 99% through Pressure Swing Adsorption to CO volume content, CO gas is forced into 6.5 MPa through compressor 2, another is that the calcium hydroxide emulsion of 200 g/L is forced into 6.5 MPa through pump 3-1 by concentration, two kinds of materials are heated to 180 DEG C with flow 24000 L (mark condition)/h and 300 L/h through preheater respectively and enter compressive reaction still 4-1, temperature control 200 DEG C in compressive reaction still, pressure 6 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.008, mixing speed is 60 rpm, react with this understanding, reaction solution autoreaction still top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 0.8.Calcium hydroxide transformation efficiency more than 99.3%, calcium formiate content 99.5% in product.
Result is investigated in embodiment 4 two compressive reaction still series connection
Adopt two compressive reaction still series connection, the CO gas that producer gas generator generates is sloughed H through refining plant by composition graphs 4
2s, CO
2deng impurity, be after 80% through Pressure Swing Adsorption to CO volume content, CO gas is forced into 6.5 MPa through compressor 2, another is that the calcium hydroxide emulsion of 200 g/L is forced into 6.5 MPa through pump 3-1 by concentration, two kinds of materials enter in series pressurized reactor 4-1 with flow 66000 L (mark condition)/h and 1000 L/h through preheater preheats to 180 DEG C respectively, as shown in Fig. 3 mode of connection, temperature control 200 DEG C in two compressive reaction stills, pressure 6 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.008, mixing speed is 60 rpm, react with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 1.2.Calcium hydroxide transformation efficiency 100%, calcium formiate content 99.5% in product.
Result is investigated in embodiment 5 two compressive reaction still parallel connections
Adopt two compressive reaction stills in parallel, adopt two-stage stirring rake in still, the rich CO gas from yellow phosphoric tail gas is sloughed H through refining plant by composition graphs 4
2s, CO
2after impurity, obtain the CO gas that CO volume content is 80%, 6.5 MPa are forced into again through compressor 2, another is that the calcium hydroxide emulsion of 200 g/L is forced into 6.5 MPa through pump 3-1 by concentration, two kinds of materials enter in compressive reaction still 4-1 in parallel with flow 72000 L (mark condition)/h and 1200 L/h through preheater preheats to 180 DEG C respectively, as shown in Fig. 2 mode of connection, temperature control 200 DEG C in two compressive reaction stills, pressure 6 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.004, mixing speed is 60 rpm, react with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 1.4.Calcium hydroxide transformation efficiency 100%, calcium formiate content 99.5% in product.
Result is investigated in embodiment 6 two compressive reaction still series connection
Adopt two compressive reaction still series connection, adopt two-stage stirring rake in still, the CO gas that producer gas generator generates is sloughed H through refining plant by composition graphs 4
2s, CO
2after impurity, be after 80% through Pressure Swing Adsorption to CO volume content, 2.5 MPa are forced into again through compressor 2, another is that the calcium hydroxide emulsion of 80 g/L is forced into 2.5 MPa through pump 3-1 by concentration, two kinds of materials enter compressive reaction still 4-1 with flow 6600 L (mark condition)/h and 150 L/h through preheater preheats to 160 DEG C respectively, in compressive reaction still 4-1, as shown in Fig. 2 mode of connection, temperature control 170 DEG C in two compressive reaction stills, pressure 2 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.004, mixing speed is 60 rpm, react with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 0.6.Calcium hydroxide transformation efficiency 99.5%, calcium formiate content 99.5% in product.
Result is investigated in embodiment 7 two compressive reaction still parallel connections
Adopt two compressive reaction stills in parallel, adopt two-stage stirring rake in still, the CO gas that producer gas generator generates is sloughed H through refining plant by composition graphs 4
2s, CO
2after impurity, be after 80% through Pressure Swing Adsorption to CO volume content, 2.5 MPa are forced into again through compressor 2, another is that the calcium hydroxide emulsion of 80 g/L is forced into 2.5 MPa through pump 3-1 by concentration, two kinds of materials enter compressive reaction still 4-1 with flow 7200 L (mark condition)/h and 180 L/h through preheater preheats to 160 DEG C respectively, as shown in Fig. 2 mode of connection, temperature control 170 DEG C in two compressive reaction stills, pressure 2 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.004, mixing speed is 60 rpm, react with this understanding, end reaction liquid autoreaction still 4-2 top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 0.6.Calcium hydroxide transformation efficiency more than 99%, calcium formiate content >99.5% in product.
Result is investigated in embodiment 8 two compressive reaction still parallel connections
Adopt two compressive reaction stills in parallel, adopt two-stage stirring rake in still, the CO gas that producer gas generator generates is sloughed H through refining plant by composition graphs 4
2s, CO
2after impurity, be after 99% through Pressure Swing Adsorption to CO volume content, 6.5 MPa are forced into again through compressor 2, separately the carbide slag emulsion containing calcium hydroxide concentration being 200 g/L is forced into 6.5 MPa through pump 3-1, two kinds of materials enter compressive reaction still 4-1 with flow 72000 L (mark condition)/h and 1300 L/h through preheater preheats to 180 DEG C respectively, as shown in Fig. 2 mode of connection, temperature control 200 DEG C in two compressive reaction stills, pressure 6 MPa, interpolation quality and the fresh hydrooxidation calcium mass ratio of reaction promotor (formic acid) are 0.004, mixing speed is 60 rpm, react with this understanding, end reaction liquid self-pressurization reactor 4-2 top overflows and enters settlement separator 6, calcium formiate mother liquor is obtained after flame filter press 7, this mother liquor isolates calcium formiate with whizzer after reduction vaporization is concentrated, then through 160 DEG C of dry finished product calcium formiates.In precipitation separation tank, unreacted calcium hydroxide is present in lower floor's solution, and turn back to compressive reaction still 4-1 through recycle pump 3-2 and continue reaction, internal circulating load and fresh hydrooxidation calcium feed liquid throughput ratio are 1.5.Calcium hydroxide transformation efficiency more than 99%, calcium formiate content >99.5% in product.
Claims (10)
1. produced a continuous production processes for calcium formiate by calcium hydroxide carbonylation, it is characterized in that the step comprised:
1) a compressive reaction still or more than one multiple compressive reaction still serial or parallel connection is used;
2) stirring rake is set in each compressive reaction still, 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 by strengthening reaction process in gas-liquid-solid between mass transfer improve speed of reaction;
3) by overflow weir, reacted material is flowed out, settlement separate method is adopted to make calcium formiate product and the initial gross separation of unreacted hydrogen calcium oxide, unreacted calcium hydroxide material flows out as the bottom of circulation fluid from subsider, is recycled in compressive reaction still and continues reaction;
4) calcium formate solution after being separated delivers to multiple-effect evaporator condensing crystal again after flame filter press filters, then via separating centrifuge separation, drying machine drying;
5) pattern of multiple compressive reaction still series connection the gas phase of first reactor outflow and liquid phase material is entered into second reactor respectively continue reaction, the liquid phase material flowed out in last reactor is delivered in settlement separator, follow-up workshop section is delivered to after utilizing calcium formiate and calcium hydroxide and impurity different solubility in water to make calcium formate solution initial gross separation, unreacted completely calcium hydroxide and partial impurities delivers to continuation reaction in first reactor by recycle pump, to guarantee calcium hydroxide complete reaction, the calcium formate solution of extraction from settlement separator enters calcium formiate mother liquor tank after impurity removes by flame filter press further, again by being pumped to multiple-effect reduction vaporization crystallizer, crystalline product liquid delivers to moisture eliminator after centrifuging, drying obtains calcium formiate solid particulate, when lower to reaction product purity requirement, do not adopt settlement separator, the thick solution of calcium formiate that reaction generates directly is entered follow-up workshop section,
6) pattern and the difference of connecting of multiple autoclave parallel connection are that the gas-phase feed of each reactor is all fresh CO (carbon monoxide converter) gas and each reactor has independently gas phase emission mouth;
7) in reactant, reaction promotor is added.
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, is characterized in that the reaction pressure of described compressive reaction still is 1.5 MPa
8 MPa.
4. continuous production processes according to claim 1, is characterized in that the service temperature of described compressive reaction still is 160 DEG C
230 DEG C.
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, is characterized in that described carbon monoxide feed gas concentration is 50%-100%.
7. continuous production processes according to claim 1, is characterized in that described calcium hydroxide and CO feeding temperature are 140 DEG C
200 DEG C.
8. continuous production processes according to claim 1, is characterized in that the temperature of described moisture eliminator is 120 DEG C
180 DEG C.
9. continuous production processes according to claim 1, is characterized in that described circulating fluid flow rate and fresh hydrooxidation calcium feed liquid throughput ratio are 0.05
5.
10. continuous production processes according to claim 1, is characterized in that described reaction promotor is one or more in formic acid, formate, oxalic acid, oxalate, sodium hydroxide, potassium hydroxide, adds quality and fresh hydrooxidation calcium 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 CN103113208A (en) | 2013-05-22 |
| CN103113208B true 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) |
Families Citing this family (12)
| 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 |
| CN103601630A (en) * | 2013-07-08 | 2014-02-26 | 曹正祥 | Method utilizing calcium carbide slag and carbon monoxide to synthesize calcium formate |
| 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 |
| 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 |
| 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 |
| 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 |
| CN109422641B (en) * | 2017-09-05 | 2021-05-14 | 天津大学 | Continuous production method for preparing calcium formate from yellow phosphorus 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 |
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》.2009,(第04期),B016-128. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103113208A (en) | 2013-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113208B (en) | The continuous production processes of calcium formiate is prepared by calcium hydroxide carbonylation | |
| EP4049748A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| CN105061165B (en) | Reaction apparatus for preparing polyoxymethylene dimethyl ether | |
| CN107522602B (en) | Process and system for preparing DMM2 | |
| CN106631684A (en) | Method for preparing SBA(sec-butyl alcohol) through hydrolysis with sec-butyl acetate | |
| CN105001185A (en) | Maleic anhydride tail gas treatment equipment and maleic anhydride tail gas treatment process | |
| CN104478644B (en) | A kind of tert-butyl alcohol is prepared the method for isobutene | |
| CN106278836A (en) | Intermediate concentration formaldehyde and the apparatus and method of methylal synthesis polymethoxy dimethyl ether | |
| CN105461515A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN104557809A (en) | Method for producing furfural from pentose | |
| 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 | |
| CN102786073B (en) | Method for preparing high-concentration calcium chloride solution by decomposing ammonium chloride with lime powder | |
| CN104119225A (en) | New technology for producing ethyl acetate through reactive distillation by taking mixed ionic liquid as catalyst | |
| CN106608832B (en) | The process of liquid ammonia process for caustic soda purification and Ammonia Process co-producing ethanol amine | |
| CN102838632B (en) | Process for continuously producing trimethyl phosphite by using N, N-dimethylaniline | |
| CN217431708U (en) | Triethylamine water removal device | |
| CN109865493A (en) | A kind of twin drum bubble column reaction unit and reaction process for p xylene oxidation | |
| CN204939338U (en) | A kind of reactive system of coking crude benzene hydrogenation technique | |
| CN114853614A (en) | Triethylamine water removal device and water removal process | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| CN111153823B (en) | Method for preparing oxamide from dimethyl oxalate | |
| CN106517132A (en) | Device and method for recycling phosphorus and magnesium from phosphorus ore magnesium removal liquid | |
| CN113248389A (en) | Production system and method of 1, 2-cyclohexanediamine | |
| CN104788284B (en) | The continuous producing method of low carbon alcohol by synthetic gas |
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 |