CN1038071A - Waste liquor of ammonia soda plant and bittern are made the method for fiber calcium sulfate - Google Patents
Waste liquor of ammonia soda plant and bittern are made the method for fiber calcium sulfate Download PDFInfo
- Publication number
- CN1038071A CN1038071A CN 89102369 CN89102369A CN1038071A CN 1038071 A CN1038071 A CN 1038071A CN 89102369 CN89102369 CN 89102369 CN 89102369 A CN89102369 A CN 89102369A CN 1038071 A CN1038071 A CN 1038071A
- Authority
- CN
- China
- Prior art keywords
- calcium sulfate
- bittern
- terra alba
- ammonia
- waste liquor
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/36—Nitrates
- C01F11/40—Preparation by double decomposition with nitrates
Abstract
1. a method that fully utilizes ammonia alkali factory evaporated waste ammonia liquid and salt manufacturing bittern is that two kinds of raw materials are generated terra alba in proportion in crystallizer, again in the reacting by heating still 105～110 ℃ of normal pressures.Thermal conversion half an hour under pH≤1 condition, promptly generate half water cellulose calcium sulfate product.This product look pure white is, even, length controlled within 0～20 micron, length-to-diameter ratio＞10.This fiber product is suitable for doing the compound of plastics industry.
Its chemical equation is as follows:
Description
The invention belongs to the comprehensive utilization of waste liquor of ammonia soda plant and salt-manufacturing waste liquor.
Big quantity research is being done aspect the processing waste liquor of ammonia soda plant by various countries at present, has the waste residue of employing to improve the soil.As the inorganic additives of poultry feed, material of construction is done the ca and mg fertilizer material.Chinese patent 87108216 provides the technology of making cement from ammonia-soda fag-end, Chinese patent 86107909 provides the method for salt and soda ash combination producing, this method had both been utilized waste liquid, salt manufacturing quality and output have been improved again, and calcium is reclaimed in continuation, magnesium, potassium, bromine, products such as gypsum, make waste liquor of ammonia soda plant and salt-manufacturing waste liquor find outlet, gypsum product in this patent is α gypsum and the β gypsum made from traditional method, the purpose of this invention is to provide and a kind ofly utilize ammonia alkali factory waste clear solution and the production of salt manufacturing bittern to be different from α, the method of the fiber calcium sulfate of β gypsum makes the comprehensive utilization of two kinds of waste liquids stride forward a step.
The method that waste liquor of ammonia soda plant of the present invention and bittern are made fiber calcium sulfate is such, with reference to accompanying drawing, ammonia alkali factory evaporated waste ammonia liquid is mixed with 1: 5～1: 10 ratio with saltern salt manufacturing bittern, promptly makes terra alba (CaSO
42H
2O) slurry, this slurry is sloughed sulphur removal bittern through dehydration, then paste terra alba slurry, add hydrochloric acid or sulfuric acid and regulate PH≤1, under normal pressure, be heated to 105～110 ℃, the boiling back promptly changes into pulpous state half water cellulose calcium sulfate (CaSO half an hour
41/2 H
2O), this pulpous state half water cellulose calcium sulfate is through washing dehydration, throwing away liquid returns in the terra alba slurry and recycles or discharge, behind the slurry fiber calcium sulfate washing dehydration moisture be 40～60% wet fiber calcium sulfate, the spray-dried again half water cellulose calcium sulfate finished product that promptly gets, sulphur removal bittern can continue to extract Chemicals.
It is to utilize calcium ion and the sulfate ion effect in the bittern of saltern in the waste ammonia-soda solution to generate terra alba that fiber calcium sulfate of the present invention is made principle, and terra alba is at acidic salt solution (CaCl
2) in be converted into the calcium sulphate hemihydrate fiber, need be heated in the conversion process between 105～110 ℃, its reaction equation is as follows:
The generation of terra alba of the present invention is to finish in the crystallization settling vessel, and two kinds of raw materials divide some groups to spray mixing in the crystallization settling vessel, and inside adds two groups of propeller pump, cause circulation, make new solution, new nucleus and old crystal seed thorough mixing are able to continuous normal operation, sedimentation device and crystallizer are one, establish internal and external casing on top, interior pipe liquid rises, and outer tube liquid descends, after solid descends, at the bottom of concentrating the paste terra alba by bucket, drag discharges.
It is to finish in reacting by heating still and the reaction e Foerderanlage that adds that terra alba of the present invention is converted into the calcium sulphate hemihydrate fiber, establish heating jacket in the reaction e Foerderanlage, keep temperature of reaction, in establish interrupted interval and stir, not only stir but also carry, prevent material discharging short circuit again, by connecting communicating pipe, guarantee that Flow of Goods and Materials is unimpeded between reacting by heating still and the reaction e Foerderanlage.
The used filter washing equipment of the present invention adopts the dynamic filter of machine teaching and research room of University Of Tianjin development; Spraying drying adopts the high speed centrifugation drying machine.
Product half water cellulose calcium sulfate of the present invention is different from traditional α type, β type calcium sulphate hemihydrate, and its difference is as follows:
1, crystalline form: traditional calcium sulphate hemihydrate is white amorphous powder, and product of the present invention is fibrous, and look pure white is evenly, and length controlled is between 0～20 micron, and it is long through than＞10.
2, production method: traditional method is that raw material crushing is arrived certain particle size, adds the water boiling or press boiling certainly about 125 ℃, and dewatered drying is ground into the end then; This law is that the thermal conversion generation must the shape calcium sulphate hemihydrate between 105～110 ℃ under normal pressure.
3, transformation time: traditional method needs 5～7 hours, only needs can transform fully half an hour and this law temperature is low.
Table 1 is the process data of indoor production calcium sulphate hemihydrate fiber.
Accompanying drawing is produced technology, the general flow chart of half water cellulose calcium sulfate for the present invention.
Embodiment 1:
Equipment:
Reactor: 400 millimeters of stainless steel φ, in establish anchor stirrer, revolution 60RPM, worm gear reducer horsepower 1.1KW.n=1400RPM, thermal source are four of 2KW electric heaters, heat transfer area 0.4m
2, heating medium is the high flash point gear oil.
The reaction e Foerderanlage: long 3 meters, revolution 70RPM, horsepower 1.1KW, in join 2 .n=1400RPM of 2KW electric heater, be placed on the bottom, two ends respectively, external diameter of pipe is 102 millimeters in the handling machinery, heat transfer area 0.8m
2
Spraying drying adopts GLP type-50 Highspeedcentrifugingandsprayingdrier, and the maximum moisture steam output is 50 kilograms/hour, and the kiln diameter is 2 meters, the centrifugal spraying head adopts mechanical transmission, and maximum speed 18000RPM, thermal source are electric energy, physical dimension is long * wide * high=4 * 3 * 4.5(M).
Processing condition:
Conversion condition: heating-surface area is 0.4m
2Be 45 minutes heat-up time.About 350 ℃ of heated oil liquid temp, 106 ℃ of heating feed temperatures add 45 kilograms/time of heats, 6～8 kilograms of solid contents.PH＝1。
Advance the still pulp density: liquid-solid ratio 1: 9(is that the boundary measures with heating liquid level half an hour).
Discharge pulp density: liquid-solid ratio 1: 6～1: 2.
The drying process with atomizing condition: feed slurry is moisture 55%, solid-to-liquid ratio 1: 1.Normal temperature, 420～430 ℃ of inlet air temperature, 160～180 ℃ of air outlet temperatures.Test each half an hour of time of drying.
End properties component content % Chemical Composition %
CaSO
4H
2O CaO SO
3H
2O
Raw material terra alba 79.07 20.95 32.56 46.51 20.92
Finished product calcium sulphate hemihydrate 93 7 38.63 55.16 6.20
The finished product physicals:
Capacity: 752.5 grams per liters
Standard consistency: 60%
Time of coagulation: initial set 5 ' 15 " final set 8 '
Tensile strength: 22.5kg/cm
2
Folding strength: 36.3kg/cm
2
Ultimate compression strength: 216kg/cm
2
The method of waste liquor of ammonia soda plant of the present invention and bittern manufacturing half water cellulose calcium sulfate, be the reprocessing of on salt and the made terra alba of pure soda combine production method basis, carrying out, this processing unit is simple, there is not high-temperature high-pressure apparatus, energy consumption is low, and easily continuous and industrialization is suitable for mass production, the product fiber calcium sulfate that this law is produced has ample scope for one's abilities as the compound in the plastics industry.
Claims (1)
1, a kind of method of making fiber calcium sulfate, it is to make terra alba earlier after being mixed by ammonia alkali factory evaporated waste ammonia liquid and salt manufacturing bittern, is converted into half water cellulose calcium sulfate by terra alba again, the present invention is characterised in that:
A, waste liquor of ammonia soda plant and bittern make the terra alba slurry with 1: 5～1: 10 mixed;
B, the paste terra alba slurry after dehydration add hydrochloric acid or sulfuric acid is regulated PH≤1, is heated to 105～110 ℃ under normal pressure, promptly changes into half water cellulose calcium sulfate the back half an hour of seething with excitement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102369 CN1038071A (en) | 1989-04-18 | 1989-04-18 | Waste liquor of ammonia soda plant and bittern are made the method for fiber calcium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102369 CN1038071A (en) | 1989-04-18 | 1989-04-18 | Waste liquor of ammonia soda plant and bittern are made the method for fiber calcium sulfate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1038071A true CN1038071A (en) | 1989-12-20 |
Family
ID=4854665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89102369 Pending CN1038071A (en) | 1989-04-18 | 1989-04-18 | Waste liquor of ammonia soda plant and bittern are made the method for fiber calcium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1038071A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122638C (en) * | 2000-12-06 | 2003-10-01 | 化学工业部连云港设计研究院 | Comprehensive utilization method of waste ammonia sode liquid and sodium sulfate containing waste liquid |
| CN102153127A (en) * | 2011-03-12 | 2011-08-17 | 广东南方碱业股份有限公司 | Method for preparing gypsum by removing sulfate radicals from mineral salts with waste distillation liquid from ammonia alkali factory |
| CN102351155A (en) * | 2011-07-12 | 2012-02-15 | 湖南恒光科技股份有限公司 | Alkali manufacturing technology for combined production of sulfuric acid and cement |
| CN102951668A (en) * | 2012-12-13 | 2013-03-06 | 国家海洋局天津海水淡化与综合利用研究所 | Method for co-producing calcium sulphate and magnesium hydrate by ammonia alkali waste liquid and concentrated seawater |
| CN106000076A (en) * | 2015-07-08 | 2016-10-12 | 黄立维 | Ferric chloride solid particles for denitration and preparation method and device thereof |
-
1989
- 1989-04-18 CN CN 89102369 patent/CN1038071A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122638C (en) * | 2000-12-06 | 2003-10-01 | 化学工业部连云港设计研究院 | Comprehensive utilization method of waste ammonia sode liquid and sodium sulfate containing waste liquid |
| CN102153127A (en) * | 2011-03-12 | 2011-08-17 | 广东南方碱业股份有限公司 | Method for preparing gypsum by removing sulfate radicals from mineral salts with waste distillation liquid from ammonia alkali factory |
| CN102351155A (en) * | 2011-07-12 | 2012-02-15 | 湖南恒光科技股份有限公司 | Alkali manufacturing technology for combined production of sulfuric acid and cement |
| CN102951668A (en) * | 2012-12-13 | 2013-03-06 | 国家海洋局天津海水淡化与综合利用研究所 | Method for co-producing calcium sulphate and magnesium hydrate by ammonia alkali waste liquid and concentrated seawater |
| CN102951668B (en) * | 2012-12-13 | 2014-09-03 | 国家海洋局天津海水淡化与综合利用研究所 | Method for co-producing calcium sulphate and magnesium hydrate by ammonia alkali waste liquid and concentrated seawater |
| CN106000076A (en) * | 2015-07-08 | 2016-10-12 | 黄立维 | Ferric chloride solid particles for denitration and preparation method and device thereof |
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| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |