CN1011402B - A kind of technology for removal of magnesium from phosphorous ore - Google Patents
A kind of technology for removal of magnesium from phosphorous oreInfo
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- CN1011402B CN1011402B CN 88105674 CN88105674A CN1011402B CN 1011402 B CN1011402 B CN 1011402B CN 88105674 CN88105674 CN 88105674 CN 88105674 A CN88105674 A CN 88105674A CN 1011402 B CN1011402 B CN 1011402B
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- slurries
- ore
- phosphorus
- magnesium
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Abstract
A kind of chemical process of relevant removal of magnesium from phosphorous ore.It is to use certain iron-holder, and 95% crosses 100 purpose ground phosphate rock, be made into the slurries of certain solid-to-liquid ratio with water, feeding contains the waste gas of sulfurous gas, pH value in the slurries is remained between 2.0～5.0, after reacting 8～24 hours at normal temperatures and pressures, analyse method etc. with sedimentation and filtration method or pen again, magniferous liquid phase is separated with the phosphorus concentrate, discharge after waste water is handled with appropriate means or use it for anything else, gained phosphorus concentrate can improve 1～7% grade, magnesium content is below 1%, and phosphorus decreases less than 5%, and this technology also has the effect of desulfurization, remarkable in economical benefits simultaneously.
Description
The present invention is the chemical process of relevant removal of magnesium from phosphorous ore.
Carbonate content height in the Rock Phosphate (72Min BPL), magnesiumcarbonate content height particularly, it is the ubiquitous problem of China's phosphorus ore, it also is one of world-famous puzzle, in the phosphorus ore when magnesian content greater than 1.5% the time, make just difficulty very of phosphoric acid, and the most of phosphorus ores of China contain magnesium oxide all greater than 1.5%, high reaches more than 10%, has seriously influenced the development of China's phosphate fertilizer industry and even whole chemical fertilizer industry.In order to develop the phosphorus industry and the chemical fertilizer industry of China, must carry out enrichment method to Rock Phosphate (72Min BPL), make content of magnesia below 1.5%.
Concentrating of Rock Phosphate (72Min BPL), traditional method have flotation process and calcining digestion method, but to high-magnesium-phosphorus ore, do not reach a standard as yet economically and qualitatively.The spissated chemical treatment method of relevant Rock Phosphate (72Min BPL), the domestic research of having reported once that HeFei University of Technology carried out with ground phosphate rock purifying low-concentration sulfurous gas, what this data was mainly said is to use ground phosphate rock under appropriate catalyst and processing condition, remove sulfur in smoke, reach the purpose of desulfurization, simultaneously, direct production phosphate fertilizer, products therefrom are single superphosphate fertilizer, the average desulfurization degree of flue gas is 90%, the average rate of decomposition of ground phosphate rock is 75%, and 25% phosphorus unreacted utilization is arranged, and is present in the single superphosphate fertilizer, gained phosphate fertilizer must carry out secondary processing to be handled, this kind method has been reported concentrating of Rock Phosphate (72Min BPL) indirectly, but needs catalysis, heat, and phosphorus decreases excessive.
The great majority of foreign patent bibliographical information are to contain the high Rock Phosphate (72Min BPL) concentration method of lime carbonate, as the clear 37-2007 of Japanese Patent, the method of being adopted is that the low-concentration sulfur dioxide with anaerobic concentrates and contains the high Rock Phosphate (72Min BPL) of lime carbonate, generate water-soluble calcium sulfite and separate, and reach the purpose of enrichment phosphorus ore with water-fast phosphorus ore.This kind method is at containing the high Rock Phosphate (72Min BPL) of lime carbonate, and it emphasizes it must is the sulfur dioxide gas of anaerobic.As adopt oxygen containing sulfur dioxide gas, and generate water-soluble calcium bisulfite so and will continue oxidation, and finally generate water-fast calcium sulfate, be present in the phosphorus concentrate, do not reach the purpose of enrichment phosphorus ore.English Patent 831916, Israel's patent 10259 and 11185 are in fact all similar with Japanese Patent, emphasize it must is the sulfur dioxide flue gas of using anaerobic.
United States Patent (USP) U.S3717702 has reported and has contained the high phosphorus ore concentration method of magnesiumcarbonate, this method is to contain 16～40%, to be 200 purpose phosphorus ores with water and sulfuric acid or sulfur dioxide gas mix fineness forms the slurries that contain solid 40～50%, the acid amount of adding is looked the pH value that keeps in the slurries between 2.0～5.0, mixed 1～3 hour, 40～65 ℃ of temperature, keep this temperature with the steam of bubbling in slurries, reacted slurries, will with contain the filter cake phosphorus ore that the magnesium liquid phase separation goes out and can filter with the usual method picture, precipitation or centrifugation, the liquid phase of gained can be abandoned it after water and other suitable liquid scrubbing, and the filter cake phosphorus ore contains that magnesium is low to can be used as raw material and join common Digestive tract gas washing in SA production phosphoric acid.With this kind method enrichment phosphorus ore, must consume more expensive sulfuric acid and the industrialness sulfur dioxide gas of a large amount of prices, poor general to China's sulphur resource, also need spend the about sulfuric acid more than 300,000 tons of a large amount of foreign exchange imports every year, is very non-remunerative, and this method needs to keep temperature of reaction at 40～65 ℃ with steam, need a cover for steam unit, and equipment is perishable, makes equipment and material are all had relatively high expectations, therefore, need further improve this technology for removal of magnesium from phosphorous ore.
The objective of the invention is to by following technical measures, solve in the demagging from phosphate ore concentration technology, because the poor general and high problem of bringing of temperature of reaction of sulphur resource.
Concrete technical measures of the present invention are: 1. control the granularity of phosphorus ore, 2. control the content of iron in the phosphorus ore, 3. phosphorus ore is made into the slurries of certain solid-to-liquid ratio, 4. feed the waste gas that contains sulfurous gas continuously, 5. react at normal temperatures and pressures.
1. control the granularity of phosphorus ore:
The granularity of phosphorus ore is to be advisable for a short time, and granularity is more little, and reaction is carried out fully more, but correspondingly the ore grinding expense also must increase, and therefore, is guaranteeing that granularity is big more economical more under the situation about reacting completely, and this law 95% can meet the demands by 100 orders.
2. the content of iron in the control phosphorus ore:
Iron reaction to carbonate in phosphorus ore plays catalyzer, and the iron-holder in the phosphorus ore should be greater than 0.5%, but the highest ratio that should make ferric oxide and Vanadium Pentoxide in FLAKES is less than 4%, and iron-holder is all in this scope in the general phosphorus ore.The content of iron is too much, then can influence the quality of phosphorus ore, and is too small, and speed of response is slowed down.Therefore, can arrange in pairs or groups mutually, make iron-holder in the phosphorus ore reach about 0.5% and get final product, if iron-holder other iron catalyst, the FeSO of adding on the low side in the phosphorus ore to different iron-holder phosphorus ores
47H
2O makes it to reach above-mentioned requirements.
3. above-mentioned phosphorus ore is made into the slurries of certain solid-to-liquid ratio:
It is 1: 4～10 that phosphorus ore is made into solid-to-liquid ratio, by magnesian content decision in the slurries, for the content of magnesia that makes the phosphorus concentrate after the enrichment less than 1.5%, the demagging effect is more satisfactory, the solid-to-liquid ratio that is made into should make content of magnesia in the reacted slurries below 13.6 grams per liters.
4. feed continuously and contain the waste gas of sulfurous gas more than 0.2%:
To be made into the phosphorus ore slurries of certain solid-to-liquid ratio, feeding contains the waste gas of sulfurous gas more than 0.2% continuously.At first, the water-soluble generation sulfurous acid of sulfurous gas, again with phosphorus ore in magnesiumcarbonate reaction owing to also contain lime carbonate simultaneously in the phosphorus ore, therefore, also with calcium carbonate reaction, its reaction formula is as follows:
Because aerobic exists in the waste gas, oxidizing reaction also takes place simultaneously, because of containing iron in the phosphorus ore, so its reaction is violent especially, and its reaction formula is as follows:
Therefore, react sulphite and the gypsum that after product is mainly water-soluble sal epsom, magnesium bisulfite, calcium bisulfite and is insoluble in water.
See theoretically, need 1 mole sulfurous gas for the carbonic acid gas of 1 mole of normal salt, but for hydrosulphite, then 1 mole of carbon dioxide needs 2 moles of sulfurous gas, carry out fully in order to make reaction, keep pH value in the slurries simultaneously between 2.0～4.0,1 mole of carbon dioxide is advisable with about 1.5 moles sulfurous gas.Therefore, the pH value that should keep according to the required sulfurous gas mole number of reaction and slurries, and the content of sulfurous gas in the waste gas, promptly may command waste gas is into and out of flow of going into reaction tower and time.
5. reaction at normal temperatures and pressures:
Because contain in aerobic and the slurries in the waste gas and contain iron catalyst, therefore, reaction can be carried out at normal temperatures and pressures, the reaction times was advisable with 8～24 hours.Improve temperature of reaction, speed of response is accelerated, and correspondingly the reaction times can shorten, and vice versa.Reaction times is best with 8～12 hours, and the time is too short, and demagging does not reach requirement, and the time is oversize, and absorption rate of sulfur dioxide is too low, does not reach the exhaust gas discharging requirement.
6. the collection of phosphorus concentrate and wastewater treatment:
With reacted slurries, be put in the settling tank, the phosphorus concentrate is removed the aqueous solution and is floated on the sulphite on phosphorus concentrate upper strata etc. owing to than the great orlop that is sunken to, and the gained throw out is the phosphorus concentrate of enrichment after the demagging.Contain sal epsom and magnesium sulfite in a small amount, calcium bisulfite, phosphoric acid salt etc. in the waste water,, it can be sent to and make the ore grinding water, also can add in a small amount Wingdale and neutralize after its acidity discharging then for the factory that general calcium workshop is arranged.With the Rock Phosphate (72Min BPL) that this method was handled, the grade of phosphorus ore can improve 1～7%, and content of magnesia is lower than 1%, and phosphorus decreases less than 5%, and the average absorption rate of sulfurous gas is 80% in the waste gas, and minimum specific absorption is not less than 70%, and gained phosphorus concentrate is suitable for makes phosphoric acid or phosphate fertilizer.
7. technical process:
Fig. 1 is a process flow sheet of the present invention.
With certain iron-holder, granularity is 95% by 100 purpose ground phosphate rock, send into slurry pond 2 with belt conveyer 1, be made into slurries by certain solid-to-liquid ratio after, stir by the return pipe of mortar pump 3 in slurry pond 2, slurries are squeezed into reaction tower 6 by mortar pump 3 uniformly, three towers are arranged with staged, and by the potential difference between tower, the slurries of reaction tower 6 flow into reaction tower 5, flow into again reaction tower 4, till the liquid level of regulation. After three towers install slurries, open simultaneously the agitator in three towers, at this moment, send continuously the waste gas that contains sulfur dioxide in reaction tower 4, waste gas is with the form of JBR and the slurries adverse current that is stirring, and the cross-flow reaction enters reaction tower 5 by reaction tower 4, enter again reaction tower 6, enter again atmosphere by reaction tower 6. When the absorptivity of the sulfur dioxide in the waste gas drops to 70%, then off and on reacted slurries are entered sedimentation basin 7 by certain speed, carry out again slurries and fall tower, at last new slurries are joined in the reaction tower 6, later on by that analogy, intermittently operated, flow into the slurries of sedimentation basin 7, remove waste water solution and float on the part sulphite etc. on phosphorus concentrate upper strata, the gained sediment is the phosphorus concentrate of enrichment after the demagging, and waste water solution can return with slurry pond or discharging in lime stone and after the modification, for the factory that general calcium workshop is arranged, it can be sent to and make the ore grinding water.
The present invention has following performance characteristics:
1. the rock phosphate in powder of crossing with this PROCESS FOR TREATMENT can improve 1～7% grade, and magnesian content is below 1%, and phosphorus decreases less than 5%.
2. owing to utilize the waste gas contain sulfur dioxide to replace payable sulfur dioxide gas, reached the treatment of wastes with processes of wastes against one another, the purpose that turns waste into wealth, the average removal efficiency of its sulfur dioxide is more than 80%, minimumly is not less than 70%, reached the requirement of national toxic emission.
3. owing to utilize the sulfur dioxide in the waste gas to come demagging, much economical with sulfuric acid or industrialness sulfur dioxide method, and with respect to the very nervous situation of China's sulphur resource, can reclaim the sulfur dioxide that is thrown in the atmosphere, increased widely the development and utilization of China's sulphur resource, the economic benefit that it is potential and social benefit are quite significant.
4. owing to can react at normal temperature and pressure, thereby so that this simple for process, equipment and material are all less demanding, and corrosivity is little, and it is low, easy to operate and stable to invest operating cost, does not have the problems such as fouling.
5. the prepared phosphorus concentrate of this technique, content of magnesia is low, and has more sulfate, can be directly used in the production of phosphoric acid, and acid consumption is few.
6. this process application scope is wide, elasticity is large, it is applicable to process carbonato ore with form waste gas of sulfur dioxide, also can process sulfur dioxide in the waste gas with carbonato ore, resemble thermal power plant's tail gas, sulfuric acid plant's tail gas, lead, zinc, copper fuse tail gas, and coking tail gas etc. all can adopt rock phosphate in powder to come desulfurization, can reach the requirement of discharging standards, and simple economy.
Embodiment 1:
Get 100 gram particle degree and be 95% by 100 purpose ground phosphate rock, its iron-holder is 0.53%, and chemical constitution is; P
2O
5: 25.19, MgO:5.42, CO
2: 9.23, being made into solid-to-liquid ratio with 0.8 premium on currency is 1: 8 slurries, feeds continuously that to contain sulfurous gas be 0.54% waste gas, making the pH value in the slurries is 3.5,15 ℃ of temperature, and pressure is normal pressure, reacted 8 hours, reaction back sedimentation and filtration method separated slurry, gained phosphorus concentrate consists of: P
2O
5: 26.11, MgO:0.70, CO
2: 2.43, Fe
2O
3: 0.51, SO
4: 11.15, the smart phosphorus ore grade after the processing improves 1%, and content of magnesia is 0.70% less than 1%, and the average absorption rate of sulfurous gas is 84%, minimumly is not less than 70%.
Embodiment 2
Get 100 gram particle degree and be 95% by 100 purpose ground phosphate rock, its iron-holder is 0.64%, and chemical constitution is: P
2O
5: 20.88, MgO:10.88, CO
2: 13.81, being made into solid-to-liquid ratio with 0.8 premium on currency is 1: 8 slurries, feeds continuously that to contain sulfurous gas be 0.54% waste gas, making the pH value in the slurries is 3.6, and temperature is 20 ℃, and pressure is normal pressure, reacted 16 hours, reaction back sedimentation and filtration method separated slurry, gained phosphorus concentrate consists of: P
2O
5: 25.8, MgO:0.32, CO
2: 0.51, Fe
2O
3: 1.01, SO
4: 1.18, phosphorus concentrate grade after the processing improves 5%, and content of magnesia is 0.32% less than 1%, and the average absorption rate of sulfurous gas is 81%, minimumly is not less than 70%.
Embodiment 3:
Other condition and embodiment 2 are just the same, and the pH value of slurries is remained on 3.8, and the reaction times is 23 hours, and the reaction back is with sedimentation and filtration method separated slurry, and gained phosphorus concentrate consists of: P
2O
5: 26.25, MgO:0.22, CO
2: 0.34, Fe
2O
3: 0.63, SO
4: 1.67, the phosphorus concentrate grade after the processing can improve 5.4%, and content of magnesia is 0.22% less than 1%, and the average absorption rate of sulfurous gas is 84%, minimumly is not less than 70%.
Claims (3)
1, a kind of technology for removal of magnesium from phosphorous ore is the slurries that ground phosphate rock and water are made into certain solid-to-liquid ratio, feed sulfur trioxide gas, pH value in the slurries is remained between 2.0～5.0, at normal temperatures, hybrid reaction for some time, reacted slurries separate magniferous liquid phase with throw out, the gained throw out is the phosphorus concentrate of enrichment after the demagging, the invention is characterized in:
1. 95% phosphorus ore is crossed 100 orders;
2. the content (in ferric oxide) of controlling iron in the above-mentioned phosphorus ore is more than 0.5%, and the highest ratio of titanium dioxide two iron and Vanadium Pentoxide in FLAKES that should make is less than 4%;
3. above-mentioned phosphorus ore is made into solid-to-liquid ratio and is 1: 4～10 slurries;
4. feed continuously and contain the waste gas of sulfurous gas more than 0.2%;
5. reacted at normal temperatures and pressures 8～24 hours;
6. in technical process, adopt the intermittent type charging and discharging, feed form waste gas of sulfur dioxide continuously.
2, technology for removal of magnesium from phosphorous ore according to claim 1 is characterized in that the content of magnesia in the reacted slurries should be less than 13.6 grams per liters.
3,, it is characterized in that the reaction times is to be advisable in 8～12 hours according to claim 1 or 2 described technology for removal of magnesium from phosphorous ore.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105674 CN1011402B (en) | 1988-02-13 | 1988-02-13 | A kind of technology for removal of magnesium from phosphorous ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105674 CN1011402B (en) | 1988-02-13 | 1988-02-13 | A kind of technology for removal of magnesium from phosphorous ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1035093A CN1035093A (en) | 1989-08-30 |
| CN1011402B true CN1011402B (en) | 1991-01-30 |
Family
ID=4833826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105674 Expired CN1011402B (en) | 1988-02-13 | 1988-02-13 | A kind of technology for removal of magnesium from phosphorous ore |
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| Country | Link |
|---|---|
| CN (1) | CN1011402B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101476049B (en) * | 2009-01-05 | 2010-06-09 | 昆明理工大学 | Method for removing magnesium from metallic ore |
| CN102442653A (en) * | 2010-09-30 | 2012-05-09 | 贵州大学 | Method for enriching P2O5 and rare-earth elements in low/middle-grade phosphorite |
| CN102838097A (en) * | 2012-09-13 | 2012-12-26 | 瓮福（集团）有限责任公司 | Method for removing magnesium oxide in phosphate concentrate through phosphatic fertilizer and phosphorus chemical industry acid wastewater |
| CN103864037B (en) * | 2014-03-21 | 2016-08-17 | 昆明理工大学 | Industrial smoke is utilized to carry out phosphorus ore de-magging and the method reclaiming phosphorus ore rare earth elements |
| CN104528781B (en) * | 2014-11-26 | 2017-01-25 | 中化化肥有限公司成都研发中心 | Method for removing sulfur dioxide in flue gas and preparing magnesium sulfate by utilizing phosphorus floatation tailings |
| CN108083243A (en) * | 2017-12-29 | 2018-05-29 | 钦州学院 | The dilute method for recycling waste acid of pyrite concentrate relieving haperacidity by-product |
-
1988
- 1988-02-13 CN CN 88105674 patent/CN1011402B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1035093A (en) | 1989-08-30 |
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