CN108249467A - A kind of method of Calcium Chloride Production good antiscale property - Google Patents

A kind of method of Calcium Chloride Production good antiscale property Download PDF

Info

Publication number
CN108249467A
CN108249467A CN201711464128.3A CN201711464128A CN108249467A CN 108249467 A CN108249467 A CN 108249467A CN 201711464128 A CN201711464128 A CN 201711464128A CN 108249467 A CN108249467 A CN 108249467A
Authority
CN
China
Prior art keywords
calcium
liquid
mother liquor
calcium chloride
chloride
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.)
Pending
Application number
CN201711464128.3A
Other languages
Chinese (zh)
Inventor
刘华军
冯敬之
于丙胜
袁庆智
高新宝
朱永智
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHANDONG OCEAN CHEMICAL IMP AND EXP CO Ltd
China National Offshore Oil Corp CNOOC
Original Assignee
SHANDONG OCEAN CHEMICAL IMP AND EXP CO Ltd
China National Offshore Oil Corp CNOOC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SHANDONG OCEAN CHEMICAL IMP AND EXP CO Ltd, China National Offshore Oil Corp CNOOC filed Critical SHANDONG OCEAN CHEMICAL IMP AND EXP CO Ltd
Priority to CN201711464128.3A priority Critical patent/CN108249467A/en
Publication of CN108249467A publication Critical patent/CN108249467A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/20Halides
    • C01F11/24Chlorides

Abstract

The invention discloses a kind of methods of Calcium Chloride Production good antiscale property, and calcium chloride concentration is not less than 15%(wt)Soda ash evaporated waste ammonia liquid as material liquid, be concentrated by evaporation by 3 effect vaporising devices, obtain calcium chloride concentration 38 42%(wt)Salt calcium among mother liquor;By mother liquor among salt calcium, sodium chloride first through physical separation removal by-product, heat preservation settlement is carried out again, obtain purer calcium liquid and the mother liquor of calcium containing crystal of calcium sulfate, abovementioned steps are returned to after mother liquor of calcium containing crystal of calcium sulfate and material liquid are mixed, control calcium chloride concentration is sent into first effect charging evaporator afterwards more than 18% (wt);By the purer calcium liquid obtained after heat preservation settlement again through 2 effect vaporising devices are concentrated by evaporation, sheeting is dried to obtain finished product two water tablets shape calcium chloride.The present invention solves the problems, such as to produce 30 days fouling 2mm originally, achievees the effect that continuous production is run 105 days and fouling thickness is no more than 0.5mm, reduce cleaning charge, improve device evaporation efficiency, greatly improve the cycle of operation of evaporator.

Description

A kind of method of Calcium Chloride Production good antiscale property
Technical field
The present invention relates to a kind of methods of Calcium Chloride Production good antiscale property.
Background technology
The production technology of country's calcium chloride at present, is the evaporated waste ammonia liquid to be generated in ammonia-soda process Sodium Carbonate Plant alkali producing process mostly For raw material, using multiple-effect vacuum vaporising device as operating unit, concentrated through multiple-effect evaporation, sedimentation separation removal sodium chloride is evaporated Liquid is completed, then complete evaporation of liquid is evaporated to the production process of concentration, sheeting drying, final products are two water tablets shape chlorination Calcium.Main production equipments are more forced-circulation evaporators, and the efficient long period continuous operation of vaporising device is Calcium Chloride Production Energy-saving key.Because of the evaporated waste ammonia liquid that the material liquid that the technique uses is ammonia-soda process soda manufacture, wherein containing a large amount of SO42- causes the evaporator heating pipe inner wall in evaporating concentration process to generate calcium sulfate scaling, seriously reduces evaporation efficiency, transports The dirty layer of row 30 days or so just needs to carry out heating tube machinery clear scar when thickening more than 2mm, thoroughly removes fouling to restore raw Production, clear scar time are 3 to 4 days, this becomes the significant bottleneck for restricting Calcium Chloride Production.Therefore slow down or prevent Calcium Chloride Production mistake The fouling of evaporator heating pipe inner wall calcium sulfate in journey is inquired into and invents a kind of method of Calcium Chloride Production good antiscale property, is steamed to improving The evaporation efficiency of device is sent out, realizes that Calcium Chloride Production industrializes continuous long-term operation, improves specific yield, energy-saving, reduction Production cost, the meaning with great reality of enhancing one's market competitiveness, be Calcium Chloride Production producer there is an urgent need to.
Invention content
There is provided a kind of methods of Calcium Chloride Production good antiscale property for the technical problems to be solved by the invention.
In order to solve the above technical problems, the present invention includes the following steps:
(1)Calcium chloride concentration is not less than 15%(wt)Soda ash evaporated waste ammonia liquid as material liquid, fed to by first evaporator Vapo(u)rization system is concentrated by evaporation by 3 vaporising devices, obtains calcium chloride concentration 38-42%(wt)Salt calcium among mother liquor;
(2)By step(1)Mother liquor among obtained salt calcium, the sodium chloride first through physical separation removal by-product, then carry out heat preservation and sink Drop, obtains purer calcium liquid and the mother liquor of calcium containing crystal of calcium sulfate, the mother liquor of calcium containing crystal of calcium sulfate is mixed with material liquid Convert rear return to step(1), the material liquid calcium chloride concentration after mixing is controlled to be sent into first effect charging evaporator afterwards more than 18% (wt);
(3)By step(2)The clear calcium liquid obtained after heat preservation settlement is again through 2 effect vaporising devices are concentrated by evaporation, sheeting is dried to obtain into Product two water tablets shape calcium chloride.
Step(2)The mother liquor of calcium composition includes:Calcium chloride 38%-42%(wt), sodium chloride 2%-7%(wt), calcium sulfate Crystallize 0.05%-0.1%(wt).
It is recycled in entire vaporising device as the calcium sulphate solid for continuing and generating of production is crystallized, the sulphur in settler Sour calcium solid crystal can constantly be enriched with increase, when calcium sulphate content reaches 0.045%-0.049% in final finished(I.e. close to product Upper limit calcium sulfate≤0.05% of standard)When, i.e., the superfluous mother liquor of calcium of enrichment is crystallized to calcium sulphate solid, is carried out periodically outer Settling tank is drained into, the supernatant liquor after sedimentation is sent again to step(1)Or step(3)Into production system, the sulfuric acid of bottom sedimentation Calcium solid crystal is finally filtered cleaning, and the outer row's period provided in the present invention is 6-7 days.
It is an advantage of the invention that:
Calcium sulphate solid crystal seed is mixed, and improve the input concentration of vapo(u)rization system by being mixed into material liquid, slow down evaporation Device heats the speed of inside pipe wall calcium sulfate scaling, solves the problems, such as to produce 30 days fouling 2mm originally, reaches continuous production operation 105 days and fouling thickness are no more than the effect of 0.5mm, substantially extend the evaporator cycle of operation.
Description of the drawings
The present invention is further described with reference to the accompanying drawings and examples:
Fig. 1 is the process flow diagram of the embodiment of the present invention.
Specific embodiment
Embodiment 1:
With reference to Fig. 1, the present embodiment uses five-effective evaporation, includes the following steps:
(1)Calcium chloride 15% will be contained(wt), sodium chloride 9%(wt)Soda ash evaporated waste ammonia liquid as material liquid, by 2nd effect evaporator It is fed as first evaporator, evaporation and concentration obtains intermediate feed liquid(One), form and include:Calcium chloride 21%(wt), sodium chloride 8% (wt), sodium chloride crystallization 4.5%(wt), crystal of calcium sulfate 0.015%(wt), it is concentrated by evaporation to obtain centre using four-effect evaporator Feed liquid(Two), form and include:Calcium chloride 34%(wt), sodium chloride 3%(wt), sodium chloride crystallization 18%(wt), crystal of calcium sulfate 0.018%(wt), concentration is evaporated subsequently into triple effect evaporator, obtains mother liquor among salt calcium, composition includes:Calcium chloride 39.5%(wt), sodium chloride 0.8%(wt), sodium chloride crystallization 23%(wt), crystal of calcium sulfate 0.02%(wt);
(2)By step(1)Mother liquor among obtained salt calcium, the sodium chloride first through physical separation removal by-product, then carry out heat preservation and sink Drop, obtains purer calcium liquid and the mother liquor of calcium containing crystal of calcium sulfate, and mother liquor of calcium composition includes:Calcium chloride 39.5%(wt), chlorination Sodium 7%(wt), crystal of calcium sulfate 0.1%(wt), the mother liquor of calcium and material liquid are mixed into rear return to step(1), control mixes Material liquid calcium chloride concentration 18.5% (wt), sodium chloride 10% afterwards(wt)It is re-fed into first evaporator evaporation;
(3)Step(2)The purer calcium liquid obtained after heat preservation settlement, composition include:Calcium chloride 40%(wt), sodium chloride 1.2% (wt), first pass through quintuple effect evaporator and be concentrated to give calcium liquid(One)Composition includes:Calcium chloride 50%(wt), sodium chloride 1.5%(wt), sulfuric acid Calcium crystallization 0.025%(wt);It is re-fed into 1st effective evaporator and is concentrated to give calcium liquid(Two)Composition includes:Calcium chloride 70%(wt), chlorination Sodium 2.1%(wt), crystal of calcium sulfate 0.035%(wt), sheeting is dried to obtain finished product two water tablets shape calcium chloride.Detect final finished, When calcium sulphate content reaches 0.045%(wt), when, calcium sulphate solid is crystallized and drains into settling tank outside the superfluous mother liquor of calcium of enrichment, is sunk Supernatant liquor after drop is sent again to step(1)Into production system, the calcium sulphate solid crystallization of bottom sedimentation is finally filtered Cleaning, the outer row's period provided in of the invention is 6 days.
Embodiment 2:
With reference to Fig. 1, the present embodiment uses five-effective evaporation, includes the following steps:
(1)Calcium chloride 15.5% will be contained(wt), sodium chloride 8.5%(wt)Soda ash evaporated waste ammonia liquid as material liquid, steamed by two effects It sends out device to feed as first evaporator, evaporation and concentration obtains intermediate feed liquid(One), form and include:Calcium chloride 22.5%(wt), chlorine Change sodium 8.5%(wt), sodium chloride crystallization 4.0%(wt), crystal of calcium sulfate 0.015%(wt), it is concentrated by evaporation using four-effect evaporator Obtain intermediate feed liquid(Two), form and include:Calcium chloride 35%(wt), sodium chloride 2.8%(wt), sodium chloride crystallization 19.5%(wt)、 Crystal of calcium sulfate 0.015%(wt), concentration is evaporated subsequently into triple effect evaporator, obtains mother liquor among salt calcium, composition packet It includes:Calcium chloride 40.8%(wt), sodium chloride 0.8%(wt), sodium chloride crystallization 23%(wt), crystal of calcium sulfate 0.02%(wt);
(2)By step(1)Mother liquor among obtained salt calcium, the sodium chloride first through physical separation removal by-product, then carry out heat preservation and sink Drop, obtains purer calcium liquid and the mother liquor of calcium containing crystal of calcium sulfate, and mother liquor of calcium composition includes:Calcium chloride 41%(wt), sodium chloride 5%(wt), crystal of calcium sulfate 0.1%(wt), the mother liquor of calcium and material liquid are mixed into rear return to step(1), after control is mixed Material liquid calcium chloride concentration 18.2% (wt), sodium chloride 10%(wt)It is re-fed into first evaporator evaporation;
(3)Step(2)The purer calcium liquid obtained after heat preservation settlement, composition include:Calcium chloride 41%(wt), sodium chloride 1.2% (wt), first pass through quintuple effect evaporator and be concentrated to give calcium liquid(One)Composition includes:Calcium chloride 51.5%(wt), sodium chloride 1.15%(wt), Crystal of calcium sulfate 0.025%(wt);It is re-fed into 1st effective evaporator and is concentrated to give calcium liquid(Two)Composition includes:Calcium chloride 71.5% (wt), sodium chloride 2.0%(wt), crystal of calcium sulfate 0.035%(wt), sheeting is dried to obtain finished product two water tablets shape calcium chloride.
Final finished is detected, when calcium sulphate content reaches 0.049%(wt), when, calcium sulphate solid is crystallized into enrichment surplus Settling tank is drained into outside mother liquor of calcium, the supernatant liquor after sedimentation is sent again to step(3)Into production system, the calcium sulfate of bottom sedimentation Solid crystal is finally filtered cleaning, and the outer row's period provided in the present invention is 7 days.

Claims (3)

  1. A kind of 1. method of Calcium Chloride Production good antiscale property, which is characterized in that include the following steps:
    (1)Calcium chloride concentration is not less than 15%(wt)Soda ash evaporated waste ammonia liquid as material liquid, imitated by head and feed evaporator and be sent into Vapo(u)rization system is concentrated by evaporation by 3 effect vaporising devices, obtains calcium chloride concentration 38-42%(wt)Salt calcium among mother liquor;
    (2)By step(1)Mother liquor among obtained salt calcium, the sodium chloride first through physical separation removal by-product, then carry out heat preservation and sink Drop, obtains purer calcium liquid and the mother liquor of calcium containing crystal of calcium sulfate, the mother liquor of calcium containing crystal of calcium sulfate is mixed with material liquid Convert rear return to step(1), calcium chloride concentration is controlled to be sent into first effect charging evaporator afterwards more than 18% (wt);
    (3)By step(2)The purer calcium liquid that is obtained after heat preservation settlement is concentrated by evaporation again through 2 effect vaporising devices, sheeting is dry To finished product two water tablets shape calcium chloride.
  2. 2. the method for Calcium Chloride Production good antiscale property according to claim 1, which is characterized in that step(2)The calcium is female Liquid composition includes:Calcium chloride 38%-42%(wt), sodium chloride 2%-7%(wt), crystal of calcium sulfate 0.05%-0.1%(wt).
  3. 3. the method for Calcium Chloride Production good antiscale property according to claim 1 or 2, which is characterized in that when sulphur in final finished When sour calcium content reaches 0.045%-0.049%, by step(2)Settling tank is drained into outside the mother liquor of calcium, the upper strata after sedimentation is clear Liquid is sent again to step(1)Or step(3)Into production system.
CN201711464128.3A 2017-12-28 2017-12-28 A kind of method of Calcium Chloride Production good antiscale property Pending CN108249467A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711464128.3A CN108249467A (en) 2017-12-28 2017-12-28 A kind of method of Calcium Chloride Production good antiscale property

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711464128.3A CN108249467A (en) 2017-12-28 2017-12-28 A kind of method of Calcium Chloride Production good antiscale property

Publications (1)

Publication Number Publication Date
CN108249467A true CN108249467A (en) 2018-07-06

Family

ID=62724560

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711464128.3A Pending CN108249467A (en) 2017-12-28 2017-12-28 A kind of method of Calcium Chloride Production good antiscale property

Country Status (1)

Country Link
CN (1) CN108249467A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3329479A (en) * 1964-04-21 1967-07-04 Hustinx Edmond Process for recovering calcium chloride from the ammonium chloride waste liquor of the ammonia soda process
US3682602A (en) * 1970-11-17 1972-08-08 Eduard Mikhailovich Mitkevich Method of producing calcium chloride and sodium chloride
SU526597A1 (en) * 1974-11-05 1976-08-30 Предприятие П/Я А-3732 Calcium Chloride Preparation Method
CN101125673A (en) * 2007-08-28 2008-02-20 唐山三友志达钙业有限公司 Method for directly producing calcium chloride from ammonia-soda process waste liquid
CN102145912A (en) * 2011-03-01 2011-08-10 大连大化工程设计有限公司 Process for preparing calcium chloride solution by utilizing ammonia soda filtration mother liquor
CN104876245A (en) * 2015-05-11 2015-09-02 华东理工大学 Method for separating sodium chloride and calcium chloride in alkali preparation waste solution by crystallization
CN105439184A (en) * 2015-12-01 2016-03-30 成都绿源新创环保科技有限公司 Resource utilization method of distilled ammonia waste liquid during sodium carbonate production and preparation system
CN104016378B (en) * 2014-05-26 2016-05-11 江苏井神盐化股份有限公司 The large crystal grain salt of a kind of low-sulfur of being produced by sodium sulfate type salt mine and production method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3329479A (en) * 1964-04-21 1967-07-04 Hustinx Edmond Process for recovering calcium chloride from the ammonium chloride waste liquor of the ammonia soda process
US3682602A (en) * 1970-11-17 1972-08-08 Eduard Mikhailovich Mitkevich Method of producing calcium chloride and sodium chloride
SU526597A1 (en) * 1974-11-05 1976-08-30 Предприятие П/Я А-3732 Calcium Chloride Preparation Method
CN101125673A (en) * 2007-08-28 2008-02-20 唐山三友志达钙业有限公司 Method for directly producing calcium chloride from ammonia-soda process waste liquid
CN102145912A (en) * 2011-03-01 2011-08-10 大连大化工程设计有限公司 Process for preparing calcium chloride solution by utilizing ammonia soda filtration mother liquor
CN104016378B (en) * 2014-05-26 2016-05-11 江苏井神盐化股份有限公司 The large crystal grain salt of a kind of low-sulfur of being produced by sodium sulfate type salt mine and production method thereof
CN104876245A (en) * 2015-05-11 2015-09-02 华东理工大学 Method for separating sodium chloride and calcium chloride in alkali preparation waste solution by crystallization
CN105439184A (en) * 2015-12-01 2016-03-30 成都绿源新创环保科技有限公司 Resource utilization method of distilled ammonia waste liquid during sodium carbonate production and preparation system

Similar Documents

Publication Publication Date Title
CN103332708B (en) A kind of Salt-nitrate coproduction method
JP4555227B2 (en) Simultaneous recovery of edible salt enriched with potassium chloride and KCl
CN105439184A (en) Resource utilization method of distilled ammonia waste liquid during sodium carbonate production and preparation system
JP4516023B2 (en) How to recover potassium sulfate
CN104528765B (en) A kind of ammonia alkali-Lian alkali cycle production process and application thereof
CN104709933B (en) Method for preparing high-purity calcium chloride by utilizing distilled ammonia waste liquid solar pond
CN105271310A (en) Chlorination-process titanium-white high-salt wastewater comprehensive utilization method
CN105417510A (en) Method for achieving ammonium chloride cooperative production through ADC foaming agent wastewater by means of total-hydrochloric acid pure hydrazine hydrate condensation
CN102502710A (en) Quintuple-effect vacuum salt production process
CN108249467A (en) A kind of method of Calcium Chloride Production good antiscale property
CN103524553B (en) The integrated conduct method of PMIDA mother liquor
CN103193252B (en) Method for producing potassium chloride by adopting carnallite hot-melt brine
CN104445337A (en) Method for preparing low-chloride gypsum by using ammonia-soda distillation waste liquid and brine
CN105366698B (en) A kind of preparation method of Magnesium sulfate heptahydrate
CN102826520B (en) Method for implementing co-production of ammonium sulfate from ADC foaming agent wastewater by extracting hydrazine hydrate
CN103073029B (en) Method for processing and producing potassium chloride by using magnesium sulfate subtype or sulfate chloride transitional-type potassium-containing salt lake brine
JP2010222242A (en) Recovery of sodium chloride and other salts from brine
CN109354038A (en) A kind of saline and alkaline joint preparation process based on ammonia-soda process
CN206244426U (en) A kind of Coal Chemical Industry strong brine sal prunella combined production device
CN105645440B (en) A kind of mirabilite hydrate produces sodium sulphate technique
CN207259304U (en) A kind of system of multistage membrane crystallization integrated treatment brine waste
CN102249268B (en) Method for enriching trace elements in saturated magnesium chloride brine by natural evaporation
CN106430248B (en) The method that potassium chloride is prepared using potassium mixed salt
CN109906200A (en) From the method for potassium chloride and gas washing in SA production potassium sulfate
CN103935971A (en) Green cycle production novel method of hydrazine hydrate, hydrazonium salts, and ADC foaming agent

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180706