CN102329215A - Method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers - Google Patents
Method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers Download PDFInfo
- Publication number
- CN102329215A CN102329215A CN201110142192A CN201110142192A CN102329215A CN 102329215 A CN102329215 A CN 102329215A CN 201110142192 A CN201110142192 A CN 201110142192A CN 201110142192 A CN201110142192 A CN 201110142192A CN 102329215 A CN102329215 A CN 102329215A
- Authority
- CN
- China
- Prior art keywords
- calcium
- chloroform
- formic acid
- hydrochloric acid
- acid
- 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
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers. The method is characterized by comprising the following steps of: diluting and dissolving chloroform leftovers with water to obtain a chloroform leftover leach liquor, feeding the chloroform leftover leach liquor, sulfuric acid, calcium formate, calcium chloride and calcium hydroxide into a corrosion-resistant reactor, reacting with stirring to generate a mixed liquid which contains formic acid, calcium sulfide and hydrochloric acid, and filtering to obtain a calcium sulfide filter cake and a filtrate, wherein the ratio of the total molar weight of the calcium formate, calcium chloride and calcium hydroxide to the molar weight of the sulfuric acid is 1:(0.8-1.2); washing the calcium sulfide filter cake, drying and smashing to obtain a calcium sulfide product; and condensing the filtrate, and filtering and separating formic acid and hydrochloric acid solutions. According to the method, pollution caused by chloroform leftovers is reduced effectively, products such as formic acid, calcium sulfide, hydrochloric acid and the like are developed, and a remarkable economic benefit is created.
Description
Technical field
The invention belongs to the technical field of organic chemistry three industrial wastes comprehensive utilization, relate in particular to the comprehensive utilization of chloroform tankage, particularly, relate to a kind of method of making formic acid co-producing sulfuric acid calcium and hydrochloric acid with the chloroform tankage.
Background technology
Adopt trichoro-aldehyde and lime to carry out alkaline hydrolysis in the industry and produce trichloromethane (chloroform), the chloroform of generation is steamed manufactures product, and remaining is exactly the chloroform tankage, is commonly called as lime cream.The staple of lime cream is calcium formiate (sub product), lime (excess raw material) and calcium chloride etc.According to calculating one ton of chloroform of every production, can produce 0.5 ton of calcium formiate.Calcium formiate is a kind of industrial chemicals of preciousness, and lime cream Chang Zuowei waste disposal, so not only waste resource, also contaminate environment.
The content of calcium formiate is 130-170 gram/L in the chloroform tankage, and calcium chloride content is 40-60 gram/L, and calcium hydroxide content is 2 gram/L, has also contained seldom the sodium-chlor of amount.The chloroform tankage are researched and developed products such as making calcium formiate, calcium chloride, calcium hydroxide will have very big economic worth.
Summary of the invention
The invention provides a kind of method with chloroform tankage manufacturing formic acid co-producing sulfuric acid calcium and hydrochloric acid, this method has effectively been administered the pollution of chloroform tankage, also develops products such as formic acid, calcium sulfate and hydrochloric acid, has created tangible economic benefit.
Technical scheme of the present invention is following: a kind of method with chloroform tankage manufacturing formic acid co-producing sulfuric acid calcium and hydrochloric acid comprises the steps:
Steps A: with the dissolving of chloroform tankage dilute with water, amount of water is controlled at and makes calcium formiate not be higher than 160g/L in the concentration of feed liquid, and postprecipitation to the solution that stirs is divided into supernatant liquid and lower sediment thing; Separate supernatant liquid and lower sediment thing, supernatant liquid is chloroform tankage leach liquor, and wherein the content of calcium formiate is 130-170 gram/L, and calcium chloride content is 40-60 gram/L, and calcium hydroxide content is 2 gram/L, also contains the sodium-chlor of minute quantity; With chloroform tankage leach liquor and sulfuric acid, with calcium formiate, calcium chloride; The molar weight sum of calcium hydroxide is that 1:0.8-1.2 drops in the corrosion resistant reactor drum with the ratio of vitriolic molar weight, and reaction under agitation generates the mixing liquid that contains formic acid, calcium sulfate and hydrochloric acid;
Step B: the mixing liquid that the steps A gained is contained formic acid, calcium sulfate and sodium sulfate is through filtering calcium sulfate filter cake and filtrating;
Step C: the calcium sulfate filter cake obtains the calcium sulfate product through washing, drying with after pulverizing;
Step D: to 6-8.3 ℃ of degree, formic acid solidifies filtrating through condenser condenses, and low temperature filters down, obtains the formic acid and second filtrating, and second filtrating is sent into and concentrated distillation in the distiller, obtains hydrochloric acid soln.
The chemical equation that technique scheme relates to is:
(HCOO)
2Ca+H
2SO
4＝＝＝＝2HCOOH+CaSO
4
CaCl
2+H
2SO
4＝＝＝＝CaSO
4+2HCl
Ca(OH)
2+H
2SO
4＝＝＝＝CaSO
4+2H
2O
Beneficial effect of the present invention is: the method with chloroform tankage manufacturing formic acid co-producing sulfuric acid calcium and hydrochloric acid according to the invention, this method has effectively been administered the pollution of chloroform tankage, also develops products such as formic acid, calcium sulfate and hydrochloric acid.
Embodiment
Embodiment 1:
A kind of method with chloroform tankage manufacturing formic acid co-producing sulfuric acid calcium and hydrochloric acid comprises the steps:
Steps A: with the dissolving of 500kg chloroform tankage dilute with water, amount of water is controlled at and makes calcium formiate not be higher than 160g/L in the concentration of feed liquid, and postprecipitation to the solution that stirs is divided into supernatant liquid and lower sediment thing; Separate supernatant liquid and lower sediment thing, obtain the 2220L supernatant liquid and be chloroform tankage leach liquor, wherein the content of calcium formiate is 160 gram/L, and calcium chloride content is 50 gram/L, and calcium hydroxide content is 2 gram/L, also contains the sodium-chlor of minute quantity; With chloroform tankage leach liquor and sulfuric acid, with calcium formiate, calcium chloride, the molar weight sum of calcium hydroxide and the ratio of vitriolic molar weight are to drop into corrosion resistant reactor drum at 1: 1, and reaction under agitation generates the mixing liquid that contains formic acid, calcium sulfate and hydrochloric acid;
Step B: the mixing liquid that the steps A gained is contained formic acid, calcium sulfate and sodium sulfate is through filtering calcium sulfate filter cake and filtrating;
Step C: the calcium sulfate filter cake obtains the calcium sulfate product through washing, drying with after pulverizing, and the pure substance quality of the calcium sulfate that it contains is 507kg;
Step D: to 6-8.3 ℃ of degree, formic acid solidifies filtrating through condenser condenses, and low temperature filters down, obtains the 368kg formic acid and second filtrating, and second filtrating is sent into and concentrated distillation in the distiller, obtains hydrochloric acid soln, and its hydrogenchloride that contains is 73kg.
Embodiment 2:
A kind of method with chloroform tankage manufacturing formic acid co-producing sulfuric acid calcium and hydrochloric acid comprises the steps:
Steps A: with the dissolving of 500kg chloroform tankage dilute with water, amount of water is controlled at and makes calcium formiate not be higher than 160g/L in the concentration of feed liquid, and postprecipitation to the solution that stirs is divided into supernatant liquid and lower sediment thing; Separate supernatant liquid and lower sediment thing, obtain the 1850L supernatant liquid and be chloroform tankage leach liquor, wherein the content of calcium formiate is 130 gram/L, and calcium chloride content is 60 gram/L, and calcium hydroxide content is 2 gram/L, also contains the sodium-chlor of minute quantity; With chloroform tankage leach liquor and sulfuric acid, with calcium formiate, calcium chloride, the molar weight sum of calcium hydroxide is that 1:1.2 drops in the corrosion resistant reactor drum with the ratio of vitriolic molar weight, and reaction under agitation generates the mixing liquid that contains formic acid, calcium sulfate and hydrochloric acid;
Step B: the mixing liquid that the steps A gained is contained formic acid, calcium sulfate and sodium sulfate is through filtering calcium sulfate filter cake and filtrating;
Step C: the calcium sulfate filter cake obtains the calcium sulfate product through washing, drying with after pulverizing, and the quality of the calcium sulfate pure substance that it contains is 387.6kg;
Step D: to 6-8.3 ℃ of degree, formic acid solidifies filtrating through condenser condenses, and low temperature filters down, obtains the 340.4kg formic acid and second filtrating, and second filtrating is sent into and concentrated distillation in the distiller, obtains hydrochloric acid soln, and its hydrogenchloride that contains is 73kg.
Embodiment 3:
A kind of method with chloroform tankage manufacturing formic acid co-producing sulfuric acid calcium and hydrochloric acid comprises the steps:
Steps A: with the dissolving of chloroform tankage dilute with water, amount of water is controlled at and makes calcium formiate not be higher than 160g/L in the concentration of feed liquid, and postprecipitation to the solution that stirs is divided into supernatant liquid and lower sediment thing; Separate supernatant liquid and lower sediment thing, obtain the 2775L supernatant liquid and be chloroform tankage leach liquor, wherein the content of calcium formiate is 150 gram/L, and calcium chloride content is 40 gram/L, and calcium hydroxide content is 2 gram/L, also contains the sodium-chlor of minute quantity; With chloroform tankage leach liquor and sulfuric acid, with calcium formiate, calcium chloride, the molar weight sum of calcium hydroxide is that 1:0.8 drops in the corrosion resistant reactor drum with the ratio of vitriolic molar weight, and reaction under agitation generates the mixing liquid that contains formic acid, calcium sulfate and hydrochloric acid;
Step B: the mixing liquid that the steps A gained is contained formic acid, calcium sulfate and sodium sulfate is through filtering calcium sulfate filter cake and filtrating;
Step C: the calcium sulfate filter cake obtains the calcium sulfate product through washing, drying with after pulverizing, and its calcium sulfate that contains is 457kg;
Step D: to 6-8.3 ℃ of degree, formic acid solidifies filtrating through condenser condenses, and low temperature filters down, obtains the 471kg formic acid and second filtrating, and second filtrating is sent into and concentrated distillation in the distiller, obtains hydrochloric acid soln, and its hydrogenchloride that contains is 58.4kg.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be regarded as belonging to the scope of patent protection that the present invention is confirmed by claims of being submitted to.
Claims (1)
1. the method with chloroform tankage manufacturing formic acid co-producing sulfuric acid calcium and hydrochloric acid is characterized in that, comprises the steps:
Steps A: with the dissolving of chloroform tankage dilute with water, amount of water is controlled at and makes calcium formiate not be higher than 160g/L in the concentration of feed liquid, and postprecipitation to the solution that stirs is divided into supernatant liquid and lower sediment thing; Separate supernatant liquid and lower sediment thing, supernatant liquid is chloroform tankage leach liquor, and wherein the content of calcium formiate is 130-170 gram/L, and calcium chloride content is 40-60 gram/L, and calcium hydroxide content is 2 gram/L, also contains the sodium-chlor of minute quantity; With chloroform tankage leach liquor and sulfuric acid, with calcium formiate, calcium chloride; The molar weight sum of calcium hydroxide is 1 with the ratio of vitriolic molar weight: 0.8-1.2 drops in the corrosion resistant reactor drum, and reaction under agitation generates the mixing liquid that contains formic acid, calcium sulfate and hydrochloric acid;
Step B: the mixing liquid that the steps A gained is contained formic acid, calcium sulfate and sodium sulfate is through filtering calcium sulfate filter cake and filtrating;
Step C: the calcium sulfate filter cake obtains the calcium sulfate product through washing, drying with after pulverizing;
Step D: to 6-8.3 ℃ of degree, formic acid solidifies filtrating through condenser condenses, and low temperature filters down, obtains the formic acid and second filtrating, and second filtrating is sent into and concentrated distillation in the distiller, obtains hydrochloric acid soln.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110142192A CN102329215A (en) | 2011-05-30 | 2011-05-30 | Method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110142192A CN102329215A (en) | 2011-05-30 | 2011-05-30 | Method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102329215A true CN102329215A (en) | 2012-01-25 |
Family
ID=45481205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110142192A Pending CN102329215A (en) | 2011-05-30 | 2011-05-30 | Method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102329215A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108946784A (en) * | 2018-08-24 | 2018-12-07 | 山西兆益生物有限公司 | A kind of mequindox mother liquor treatment process |
| CN113104869A (en) * | 2021-04-28 | 2021-07-13 | 龙岩紫云化学科技有限公司 | Method for producing magnesium hydroxide and coproducing dihydrate gypsum |
-
2011
- 2011-05-30 CN CN201110142192A patent/CN102329215A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108946784A (en) * | 2018-08-24 | 2018-12-07 | 山西兆益生物有限公司 | A kind of mequindox mother liquor treatment process |
| CN113104869A (en) * | 2021-04-28 | 2021-07-13 | 龙岩紫云化学科技有限公司 | Method for producing magnesium hydroxide and coproducing dihydrate gypsum |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101381091B (en) | Waste molten salt processing method | |
| CN101850992A (en) | Method for preparing calcium carbonate and co-producing sodium sulfate by using phosphorus gypsum and soda ash | |
| CN104477960B (en) | A kind of production method of potassium alum | |
| CN103058158A (en) | Method for preparing monopotassium phosphate from fertilizer grade calcium hydrophosphate | |
| CN102329215A (en) | Method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers | |
| CN103395816A (en) | Process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle | |
| CN104445281B (en) | Trichlorosilane elution circuit waste residue method of comprehensive utilization | |
| CN102115130A (en) | Method for preparing industrial barium chloride from barium slag | |
| CN102329216A (en) | Method for preparing formic acid coproduced with calcium chloride and sodium chloride from chloroform leftovers | |
| CN103359700A (en) | Method for saving acid and reducing ammonium in ammonium phosphate production | |
| CN101823730A (en) | Method for simultaneously producing sodium thiocyanate and ammonium carbonate | |
| CN102329214A (en) | Method for producing formic acid and coproducing calcium phosphate and hydrochloric acid by using chloroform leftovers | |
| CN102329213A (en) | Method for preparing formic acid coproduced with calcium sulfide and hydrochloric acid from chloroform leftovers | |
| CN101830493A (en) | Method for processing waste salt slurry of calcined soda with sodium carbonate and sodium sulfate | |
| CN104310364A (en) | Comprehensive utilization method of phosphoric acid sludge | |
| CN102030353A (en) | Method for preparing gypsum and simultaneously producing sodium sulfate and hydrochloric acid by distilled ammonia waste liquid of sodium carbonate | |
| CN102329219A (en) | Method for preparing calcium formate coproduced with sodium chloride and sodium hydroxide from chloroform leftovers | |
| CN102774884B (en) | A kind of method fully utilizing sulfate process titanium dioxide black mud | |
| CN102329217A (en) | Method for preparing formic acid coproduced with calcium nitrate and hydrochloric acid from chloroform leftovers | |
| CN102249340A (en) | Method for preparing manganese sulfate, manganese phosphate and calcium sulfate | |
| CN102115207A (en) | Method for producing ferrous carbonate and ammonium sulfate by using waste acid obtained during production of titanium pigment by adopting sulfuric acid process | |
| CN101767837A (en) | Method for removing titanium in ferrous sulfate as titanium dioxide byproduct | |
| CN103451434B (en) | A kind for the treatment of process of Tungsten smelting dephosphorization slag | |
| CN102329218A (en) | Method for producing sodium formate and coproducing calcium carbonate and sodium hydroxide by using chloroform leftovers | |
| CN101913643A (en) | Method for preparing strontium hydroxide and coproducing calcium sulfate dihydrate from barium sulfide waste residue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 523000, room five, building 508, Jinhai building, Dongcheng District Tong Road, Dongguan, Guangdong Applicant after: Wang Jiaxing Address before: Wushi Village Primary School in Dongguan city of Dongcheng District province Guangdong road 523000 Lane 1 No. 6 main mountain Applicant before: Wang Jiaxing |
|
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120125 |