CN100424026C - Method for combined production of gypsum, active carbon, and copperas by using waste sulfuric acid and carbide slag - Google Patents
Method for combined production of gypsum, active carbon, and copperas by using waste sulfuric acid and carbide slag Download PDFInfo
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- CN100424026C CN100424026C CNB2005100777181A CN200510077718A CN100424026C CN 100424026 C CN100424026 C CN 100424026C CN B2005100777181 A CNB2005100777181 A CN B2005100777181A CN 200510077718 A CN200510077718 A CN 200510077718A CN 100424026 C CN100424026 C CN 100424026C
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- hydrochloric acid
- filter cake
- copperas
- filtrate
- carbide slag
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/266—Chemical gypsum
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Acetylene sludge is preprocessed, and then purifying reaction is carried out on the preprocessed acetylene sludge and hydrochloric acid according to certain proportion. A black filter cake is obtained through liquid-solid separation, and refined active carbon is removed; synthesis reaction is carried out on filtrate calcium chloride and waste sulphuric acid according to certain proportion. Filtrate hydrochloric acid is obtained through liquid-solid separation and is circularly utilized; dried gypsum (plaster) is obtained after a white filter cake is washed, dehydrated, dried, calcined, pulverized, packaged, etc. In addition, when saturated, ferrous sulfate (copperas) in circulation liquid generated in the synthesizing process is cooled to be crystallized into iron vitriol (copperas) at certain temperature. The plaster is mainly used for building materials, decorative precast products, gelling agents, etc. The active carbon is mainly used for decoloring agents and odor-removing agents in chemical industry, gas masks, etc. The copperas is mainly used for treating water, manufacturing inorganic pigments, etc. The chemical reaction principle is shown below: Ca(OH)2+2HCl=CaCl2+2H2O, CaCl2+H2SO4=CaSO4+2HCl.
Description
The present invention relates to the production method of Application in Chemical Engineering technical field inorganic salts, is a kind of sulfur waste acid of titanium dioxide and the carbide slag coproduction gypsum of dissolved acetylene factory, activated carbon, method of green vitriol utilized by it.
Learning the process of producing gypsum from existing technology, is with calcium chloride and two kinds of solution of ammonium sulfate, carries out liquid phase reaction in the normal state and makes, and is commonly called as chemical precipitation method.
The present invention researches and develops successfully on the basis of chemical precipitation method.Its gordian technique is to utilize chemical sludge and the waste liquid purifying treatment by hydrochloric acid, recycle.Promptly can remove black carbon powder impurity and be refined into activated carbon, can reduce production costs by the recycle raw material again,, there is no this type of technology at home and abroad and exist through patent retrieval.
The object of the invention is to handle the sulfur waste acid of titanium powder plant and the carbide slag of dissolved acetylene factory, this is the good approach that turns waste into wealth, because acid of reasonable use sulfur waste and carbide slag not only can be country and a large amount of processing costs of enterprise's saving, and can also eliminate waste material and pile up occupation of land, the hidden danger of environmental pollution.And by the coproduction gypsum, activated carbon, three kinds of products such as green vitriol.Effectively reduced production cost, remarkable social benefit has promptly been arranged, tangible economic benefit has been arranged again.The present invention is suitable for each sulfuric acid method titanium pigment manufacturing enterprise, enterprises such as acetylene vapor phase process polyvinyl chloride industry and dissolved acetylene factory.
Technology contents of the present invention and feature:
A, pre-treatment: is calcium hydroxide content 60-80%, and water content is the carbide slag of 30-40%, with service water by 1: 1-6 is mixed in the pre-treatment jar that has agitator, stir and became uniform emulsion in ten minutes, static again two minutes, get its suspension, discard sedimentary thick property impurity.
B, purifying treatment: obtaining through pretreated carbide slag, by 1: 0.4-0.72 is mixed in 30% hydrochloric acid soln that purifies in the still, stirs and generates the calcium chloride mixing solutions in ten minutes.Through its clear liquor of leaching, but and black filter cake refined using active carbon.
C, product are synthetic: with the sulfur waste acid of the calcium chloride clear liquor that obtains and 9-12% by 1: 1-1.82 is mixed in the synthesis reactor, carries out building-up reactions and generates two H 2 O calcium sulphates and hydrochloric acid mixed solution.Obtain white filter cake after filtration and carry out deep processing, filtrate is then returned purification section and is recycled.
D, gypsum are made with extra care: the white filter cake that will obtain washs, and dehydration, drying, are calcined and obtained calcium sulphate hemihydrate in two hours in stove at 120 ℃ of-130 ℃ of temperature lower calcinations, and through pulverizing, operations such as packing obtain plaster of Paris finished product.
The processing of E, green vitriol: the filtrate that synthesizing section is obtained, reach full fashionable through repeatedly recycling when ferrous sulfate, put into 0 ℃ of cooling under-10 ℃ of temperature, in the crystallizer tank, iron vitriol can be separated out automatically, through separate the green vitriol crystal, remaining liq hydrochloric acid then returns purification section and recycles.
F, activated carbon are refining: the black filter cake that purification section is obtained, fully react with 30% hydrochloric acid again, till the pH value that makes solution is 6.5-7, get the black filter cake after filtration, by washing, dehydration, splashing, drying, packing etc. is refined into activated carbon, and filtrate is then returned synthesizing section and is recycled.
Advantage of the present invention and positively effect:
The present invention can solve the sulfur waste acid of titanium powder plant up hill and dale, also has the accumulation of acetylene vapor phase process polyvinyl chloride industry and dissolved acetylene factory carbide slag to take up an area of problems such as environmental pollution.And can be country and a large amount of processing costs of enterprise's saving.Because three kinds of Chemicals of the present invention's energy coproduction, hydrochloric acid aborning can also recycle.So the present invention has remarkable social benefit and economic benefit, also have the investment little, instant effect, benefit advantages of higher.
Accompanying drawing-illustrate is represented with block schematic diagram according to distribution of present device workshop section and Technology.Be the basic framework figure of accompanying drawing two.
1. the 2. sulfur waste acid 4. 5. 6. 7. 8. 9. activated carbon finished product of plaster stone finished product of green vitriol finished product of sulfuric acid weighing apparatus solution of sulfuric acid mixture liquid of calcium chloride of hydrochloric acid that 3. circulates of hydrochloric acid
Accompanying drawing two explanation: be the process flow diagram that the principles of chemistry and device distribution are represented according to the present invention.
①④⑥⑨ ( 11 ) ( 13 )-②③⑤⑦⑧⑩ ( 12 ) ( 14 ) ( 15 ) ( 16 ) ( 17 ) ( 18 ) ( 19 ) ( 20 ) ( 21 ) ( 22 ) ( 23 ) ( 24 ) ( 25 ) ( 26 ) ( 27 ) ( 28 ) ( 29 ) ( 30 ) ( 31 ) ( 32 ) ( 33 ) ( 34 ) ( 35 ) ( 36 )
Embodiment
(two explanations in conjunction with the accompanying drawings)
Can discharge 30,000 tons of sulfur waste acid as the annual production of certain sulfuric acid method titanium pigment factory, its average content is 9-12%, 20,000 tons of carbide slags of the annual discharging of certain acetylene method polyvinyl chloride industry, wherein calcium hydroxide content is 60-80%, water content is 30-40%, both change into gypsum, green vitriol, three kinds of joint product of gac in conjunction with repealing by implication.
Earlier carbide slag (24) being added water (23) by 1:3 is mixed in the pre-treatment jar (3), carry out pre-treatment thereby obtain evenly trickle emulsion (25), then be mixed in by 1: 0.75 with 30% hydrochloric acid soln (29-30) again and purify in the still (20), reaction generates calcium chloride (31) mixing solutions, get black filter cake (27) refined using active carbon (7) after filtration, and filtrate (31) is mixed in the dried synthesis reactor (19) by 1: 1 with the sulfur waste acid (32) of 9-12% again, and reaction generates the mixed solution of two H 2 O calcium sulphates and hydrochloric acid.(21) get filtrate (33) and return use after filtration, and white filter cake (34) is by washing, dehydration, dry (15), under 120 ℃ of-130 ℃ of temperature, place calcining furnace (16), calcine and obtained calcium sulphate hemihydrate in two hours, through pulverizing, packing is refined into the plaster of Paris (36), the black filter cake (27) that purification section gets off, neutralizing once more through hydrochloric acid (26) makes pH value reach 6.57, (22) after filtration, wash, dewater, splashing, dry (15), packing is refined into activated carbon (35).When the ferrous sulfate (33) of purification section recycle mixed solution reaches full fashionable by vacuum concentration (18), put into 0 ℃ of crystallisation by cooling groove (12) lining under-10 ℃ of temperature and carry out crystallization, obtain the green vitriol crystal through separation, drying, remaining liq hydrochloric acid (29) then returns the purification section recycle.
The embodiment of the invention:
Method one, earlier be 60-80% with calcium hydroxide content, water content is that the carbide slag of 30-40% carries out pre-treatment, obtains evenly trickle emulsion, is mixed in by 1: 0.56 with 30% hydrochloric acid soln and purifies in the still reaction generation calcium chloride mixing solutions.Get black filter cake refined using active carbon after filtration.And clear liquor is mixed in the synthesis reactor by 1: 1.41 with the acid of the sulfur waste of 9-12% again, reaction generates two H 2 O calcium sulphates and hydrochloric acid mixed solution, after filtration filtrate Returning utilization and white filter cake through washing, dehydration, dry 120 ℃ of-130 ℃ of calcination in stove two hours, calcium sulphate hemihydrate.Through pulverizing, packing is refined into 92% the plaster of Paris again.In addition, to make pH value be 6.5-7 to the black filter cake that purification section gets off through neutralization once more, more after filtration, washs, dewaters, splashing, drying, pulverizing, and operations such as packing are refined into activated carbon.The ferrous sulfate of the circulating liquid that gets off when purification section reaches full fashionable by vacuum concentration, can put in 0 ℃-10 ℃ the crystallisation by cooling groove, when treating that iron vitriol is all separated out, separate the green vitriol crystal, remaining liq hydrochloric acid is Returning utilization then.
Method two is 60-80% with calcium hydroxide content earlier, and water content is that the carbide slag of 30-40% carries out pre-treatment.Obtain evenly trickle emulsion, be mixed in the purification by 1: 0.7 with 30% hydrochloric acid soln again, reaction generates the calcium chloride mixing solutions, get black filter cake refined using active carbon after filtration, and clear liquor mixes in the dried synthesis reactor by 1: 1.41 with the sulfur waste acid of 9-12% again.Reaction generates two H 2 O calcium sulphates and hydrochloric acid mixed solution.After filtration the filtrate Returning utilization, and white filter cake is through washing, dehydration, drying, 120 ℃ of-130 ℃ of calcination in stove two hours calcium sulphate hemihydrate, again through pulverizing, the packing system is smart to become 93% the plaster of Paris.In addition, to make pH value through neutralization reaction once more be 6.5-7 to the black filter cake that gets off of purification section.Filter filter cake through wash, dewater, operation refined using active carbon such as splashing, drying, pulverizing, packing.The ferrous sulfate of the circulating liquid that gets off when purification section reaches full fashionable by vacuum concentration, can put in 0 ℃-10 ℃ the crystallisation by cooling groove, when treating that July, aqueous ferrous sulfate was all separated out, separate the green vitriol crystal, remaining liq hydrochloric acid is Returning utilization then.
Claims (2)
1. the method with sulfur waste acid and carbide slag coproduction gypsum and activated carbon and green vitriol is characterized in that comprising the steps: to be 60-80% earlier to calcium hydroxide content, and water content is that the carbide slag of 30-40% carries out pre-treatment; Be mixed in by 1: 0.4～0.72 with 30% hydrochloric acid and purify in the still, reaction generates the calcium chloride mixing solutions; After filtration the black filter cake remove refined using active carbon, and filtrate is mixed in the synthesis reactor by 1: 1～1.82 with the acid of the sulfur waste of 9-12% again, reaction generation two H 2 O calcium sulphates and hydrochloric acid mixed solution; Get the filtrate Returning utilization after filtration, and white filter cake through washing, dehydration, dry under 120 ℃ of-130 ℃ of temperature calcination in stove, calcine and got calcium sulphate hemihydrate in two hours, again through pulverizing, be packaged to be the plaster of Paris, the black filter cake once more with in 30% the hydrochloric acid and complete reaction make the pH value reach 6.5-7, the Returning utilization that filters to get filtrate, and filter cake through washing, dehydration, expanded, dry, pulverize, pack, be refined into activated carbon; When ferrous sulfate in the liquid that recycles reaches full when closing concentration by vacuum concentration, put into crystallisation by cooling groove under 0 ℃ of-10 ℃ of temperature, when treating that iron vitriol is all separated out, through separate the green vitriol crystal; Remaining liq hydrochloric acid is Returning utilization then.
2. the method for claim 1 is characterized in that described pre-treatment is is 60-80% calcium hydroxide with content, and the carbide slag of water content 30-40% is by 1: 2---6 adds water and mixes, stir and became uniform emulsion in ten minutes, static again two minutes, get its suspension, discard the thick property impurity of precipitation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100777181A CN100424026C (en) | 2005-06-24 | 2005-06-24 | Method for combined production of gypsum, active carbon, and copperas by using waste sulfuric acid and carbide slag |
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| CNB2005100777181A CN100424026C (en) | 2005-06-24 | 2005-06-24 | Method for combined production of gypsum, active carbon, and copperas by using waste sulfuric acid and carbide slag |
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| CN1884173A CN1884173A (en) | 2006-12-27 |
| CN100424026C true CN100424026C (en) | 2008-10-08 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624180B (en) * | 2009-03-03 | 2012-08-15 | 王嘉兴 | Material circulating method formed in chlor-alkali industry by using waste carbide slags and chlorine water |
| CN101830492A (en) * | 2009-06-08 | 2010-09-15 | 王嘉兴 | Material recycling method in calcium carbide industry |
| CN101851074A (en) * | 2009-06-08 | 2010-10-06 | 王嘉兴 | Method for manufacturing main cement material, additive and silicate cement by using carbide slag |
| CN101844880A (en) * | 2009-07-17 | 2010-09-29 | 王嘉兴 | Method for producing cement main material, cement auxiliary material and cement by using carbide residue |
| CN102030353A (en) * | 2010-04-30 | 2011-04-27 | 汪晋强 | Method for preparing gypsum and simultaneously producing sodium sulfate and hydrochloric acid by distilled ammonia waste liquid of sodium carbonate |
| CN102153125A (en) * | 2010-12-07 | 2011-08-17 | 何侠 | Method for preparing sulfates from pyrite cinders by chemical method |
| CN105645453A (en) * | 2015-12-14 | 2016-06-08 | 河南开祥精细化工有限公司 | Method for disposing industrial waste sulfuric acid by utilizing carbide slag |
| CN106311719B (en) * | 2016-08-22 | 2018-09-11 | 四川龙蟒钛业股份有限公司 | A kind of recoverying and utilizing method of carbide slag |
| CN107244867A (en) * | 2017-05-31 | 2017-10-13 | 安徽华塑股份有限公司 | A kind of method that sulfur waste acid treatment waste residue produces gypsum |
| CN109336159A (en) * | 2018-11-09 | 2019-02-15 | 陕西黑猫焦化股份有限公司 | Acetylene-formaldehyde process produces waste acid treatment technique caused by 1,4- butanediol |
| CN111822480A (en) * | 2020-05-22 | 2020-10-27 | 西北矿冶研究院 | Method for removing carbon in waste carbide slag |
| CN113698038A (en) * | 2021-09-01 | 2021-11-26 | 山东凯翔生物科技股份有限公司 | Utilization and treatment method of gluconolactone high-salt ion exchange wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183381A (en) * | 1996-11-25 | 1998-06-03 | 孙钧儒 | Method for producing gypsum, table salt and magnesium chloride from calcium-cantg. waste liquid and high- and low-temp. salt |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183381A (en) * | 1996-11-25 | 1998-06-03 | 孙钧儒 | Method for producing gypsum, table salt and magnesium chloride from calcium-cantg. waste liquid and high- and low-temp. salt |
Non-Patent Citations (2)
| Title |
|---|
| 硫酸法钛白生产中的废硫酸治理. 法浩然.涂料工业，第1999年第9期. 1999 |
| 硫酸法钛白生产中的废硫酸治理. 法浩然.涂料工业，第1999年第9期. 1999 * |
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Assignee: Guangzhou Built-To-Last Chemical Industry Co., Ltd. Assignor: Wang Jiaxing Contract record no.: 2010440000929 Denomination of invention: Method for combined production of gypsum, active carbon, and copperas by using waste sulfuric acid and carbide slag Granted publication date: 20081008 License type: Exclusive License Open date: 20061227 Record date: 20100708 |
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Granted publication date: 20081008 Termination date: 20110624 |