CN101439867B - Method for extracting potassium carbonate from cabo and refining carbon - Google Patents

Abstract

The invention provides a method for extracting potash and refined charcoal through the briquetting carbonization and gasification of cabo and tobacco leaves, charcoal acid cleaning or water washing. Through the procedures of cabo charcoal making, potash, refined charcoal, and the like, potash and refined charcoal are obtained by means of dissolution, filtration, concentration and crystallization. The process flow has simplicity, low investment and low production cost. Organic chemical products such as nicotine are obtained through the process of the briquetting carbonization and the gasification of the cabo and tobacco leaves, and simultaneously the fuel of wood gas is also obtained. The obtained products comprise the following organic compounds: potash, refined charcoal, potassium sulfate, potassium nitrate, potassium chloride, wood gas, nicotine, and the like.

Description

The method of a kind of extracting potassium carbonate from cabo and refining charcoal

Technical field

The present invention relates to chemical engineering class utilisation technology, offal, tobacco leaf briquetting carbonization gasification specifically, the method for salt of wormwood, refining charcoal is extracted in charcoal pickling or washing.

Background technology

Salt of wormwood can be widely used in: inorganic industry is used to make Seignette salt, aluminium potassium fluorozirconate, potassium sulfocyanate, titanium dioxide.Medicine industry is used to make medicines such as long-acting sulfanilamide, Progesterone, cortisone, Orthocoll, progynon B.Glass is warded off industry and is used for the enamel frit preparation, adds in the glass and plays fluxing action, and improve glass transparent degree and refraction coefficient.Dyestuffs industries is used to make cloudy red native woods, Disperse Red 3B, Vat Grey M etc.; Rubber industry is used to make 4010 anti-aging agent; The numb cotton industry of hair is used for cotton boiling-off and woolen degreasing.

The production technique of existing salt of wormwood has plant ash method, leblanc process, electrolytic process, amine process, ion exchange method, electrolysis with ion-exchange film---methods such as carborization, ion exchange method.The plant ash method is main and use various plant shells, as cotton seed hulls, tea shell etc., is fired into plant ash, separated respectively with leaching, evaporation, crystalline method, this method because of raw material from agricultural-food, be difficult for scale operation.Leblanc process is that vitriolate of tartar, coal dust, Wingdale are mixed by a certain percentage, adds water and stirs, and roasting becomes grey black, with hot water leaching, carbonization etc.Though plant ash is easy to obtain in the plant ash method, be difficult to collect, compiling costs is too high, and its potassium content is low, causes production cost to increase thus.Electrolytic process is with the Repone K electrolysis, obtains potassium hydroxide, then with CO ₂Carbonization gets the saleratus crystallization.Crystal just can obtain prepared calcium carbonate potassium finished product after washing, centrifugation, calcining.The electrolytic process quality product is better, but production energy consumption is too high, does not obtain large-scale application and promotes.Amine process is raw material with Repone K, and organic amine (as Isopropylamine, triethylamine, bad pregnancy imines etc.) etc. changes into salt of wormwood hydrogen potassium as carrier carbon.This method utilization ratio can reach 95%.Have that technical process is simple, with short production cycle, less energy consumption, low, the product purity advantages of higher of cost, but because lower boiling organic amine toxicity is big, both need heat steaming amine in the regenerative process, producing liquid calcium chloride again effluxes, cause environmental pollution, and the price height, limited its application to a certain extent.Ion exchange method is to be succeeded in developing by the Shandong Province beginning of the seventies, and the development of China's salt of wormwood industry is had vital role.Present domestic most salt of wormwood factory adopts this method.This method is a raw material with bicarbonate of ammonia, Repone K mainly, makes saleratus and ammonium chloride solution by Zeo-karb, and effluent liquid is calcined in calcining furnace and got product after evaporation concentration, carbonization crystallization, centrifugation, washing.This method major advantage is that technical process is simple, and raw material is easy to get, good product quality, and technology maturation is reliable, can make full use of the superfluous ammoniacal liquor in the production of synthetic ammonia and the carbon dioxide gas of unnecessary emptying.Main drawback: (1) unstable product quality, top grade, electronic grade product only about 50%.All the other I and II product prices are low, sell more not freely, restricted development.(2) the potassium ion source is Repone K, and cost is higher.(3) produce a large amount of side product sodium chloride waste water in the production process, concentration is between 8%-10%, and is too low because of concentration, corrosion is big, is difficult to recycle, and causes environmental pollution, and energy consumption is also high, does not meet the cleaner production requirement.Electrolysis with ion-exchange film--carborization is the technology that world developed country generally adopts, disposable carbonization, calcination, the exsiccant fluidized bed plant finished, production automation degree height.Main drawback is that investment is big, and the production cost height needs introduction of foreign technology and equipment and energy consumption high, and these all restrict application and the development of electrolysis with ion-exchange film carborization in China's salt of wormwood industry.

The charcoal end-use is extensive, demand constantly increases.Charcoal product purposes in national economy is very extensive: metallurgical industry: be production high-quality steel, the smeltery need be with a large amount of charcoals, and the iron and steel of smelting with charcoal is impure few, has fine-grain structure, and foundry goods is tight, does not have advantages such as crackle.In non-ferrous metal was produced, charcoal was commonly used for surperficial fusing assistant, both can reduce the spatter loss of molten metal, can reduce the saturation ratio of gas in the melts again.A large amount of charcoals also are used for silicon metal production, but the charcoal that the production silicon metal is used should not contain living charcoal head and too much ash content.Chemical industry: charcoal is a best raw material of making dithiocarbonic anhydride, is used for making the charcoal of dithiocarbonic anhydride, should be hard, volume big, ash content and moisture content are little, fixed carbon content height.Constantly soaring with the charcoal amount as the charcoal ink factory of material additive or fusion agent, gac factory, carborundum factory, silicon factory, Steel Plant, dithiocarbonic anhydride factory, explosive factory, mosquito-repellent incense factory, lagging material factory, fireworks and firecrackers factory etc. with charcoal, the situation that supply falls short of demand appears in certain areas.In addition; civilian and food-processing industry; as being used for food-processing, environment protection (charcoal, gac all have the various materials of absorption and the function of adsorbent takes place) etc., gac all has application in industries such as tap water processing, sugaring, wine brewing, medicine, printing, agriculturals.And the husbandry aspect also has been widely used.

Machine-made carbon is compared with common local method charcoal, and it is long to have a combustion time, carbon content height, characteristics such as thermal value is big, and ash is little, and is smokeless, tasteless, nontoxic.Machine-made charcoal sell well, purposes are big.Machine-made charcoal is better than local method charcoal, former charcoal, and carbon content can reach about 83%, and the carbon content of offal charcoal is about about 59%, and combustion time is long, and offal charcoal thermal value can reach 5500Kcal/Kg, and is suitable with standard coal.Be a kind of rare artificial fuel, after the major technique solution along with briquetting press, greatly reduce the production cost of machine-processed carbon, progressively move towards the industrialization.

The original applications of charcoal is a fuel, because inflammable, the anti-combustion of charcoal, ash content are few, characteristics such as sulfur-bearing not, so be a kind of fine fuel always.At the sphere of life charcoal is optimized fuel, particularly machine-made carbon such as heating, barbecue, chafing dish, because it is through the high temperature refining, thus be smokeless, nontoxic, free from extraneous odour, dryness-fire star not during burning, ash content is low, and thermal value is big, and combustion time is long, more and more is subjected to people and favors.

Summary of the invention

The purpose of this invention is to provide a kind of offal, tobacco leaf briquetting carbonization gasification, the method for extracting salt of wormwood, refining charcoal is washed or washed to wooden carbonic acid.

The present invention can be in offal, the carbonization of tobacco leaf briquetting, gasification organic chemical industry's products such as extraction nicotine, eggplant Buddhist nun alcohol, obtain fire-bote coal gas simultaneously.

Technical scheme of the present invention is:

1, offal charcoal processing:

1) broken, dry, gather dust and briquetting: the raw material offal is dried through after the fragmentation, and water content is less than 20%, and drying temperature is controlled at below 70 ℃, and tail gas is through emptying after the dedusting; The exsiccant offal is collected back briquetting in the briquetting press;

2) charing, gasification: the offal piece is added into and carries out drying, gasification, charing in the carbonization kiln; Drying temperature in 150 ℃, 1-2 hour time of drying; When temperature continues to rise, when surpassing 275 ℃, raw material begins to accelerate to decompose, along with temperature raises, decomposition rate is accelerated, and generates a large amount of resolvents, as methane, ethane, nicotine etc., simultaneously under anaerobic conditions also produce CO gas, this phase temperature remains to 400～450 ℃, obtains charcoal, wood gas, nicotine product; 550～600 ℃ of temperature controls obtain the offal charcoal, contain CO, wood gas inflammable gas and the nicotine of CH4 and H2;

3) nicotine recovery of oil and inflammable gas are collected: reclaim nicotine, inflammable gas is cooled to below 70 ℃, enters gas-liquid separator then and removes phlegma, enters alkali cleaning again, removes the impurity in the combustion gas, passes through foam removal, pressurizes, sends in the gas storage holder;

2, the preparation of salt of wormwood, refining charcoal:

1) the offal charcoal broken and gather dust, powdered carbon slurrying: with the offal charcoal after the fragmentation under agitation condition with hot water thorough mixing in extraction tank, thereby make salts such as salt of wormwood soluble in water, aqueous solvent can come from follow-up filtration washing water and filtrate, solvent temperature is 80～90 ℃, a large amount of salts such as salt of wormwood are dissolved in the liquid phase, and the control carbon content is at 25-28%;

Perhaps utilize the metallic salt in nitric acid, sulfuric acid, the dissolving with hydrochloric acid charcoal, obtain corresponding metal nitrate, vitriol, hydrochloride, the add-on of acid is pressed the mol amount summation of carbonate in the charcoal, phosphate radical and metal-salt and is calculated adding, and the free acid content in the maintenance slip is 2% ± 0.5;

2) charcoal is starched and filtered and washing: the filter cake after the charcoal slurry filters washs water temperature: 80～85 ℃ three times with the 1.5-2 times of water yield of charcoal amount;

3) filtrate evaporation concentration, crystallisation by cooling, Crystallization Separation, crystallizing and drying: get clear liquid after filtrate is left standstill through insulation and deliver to vaporizer, with forced circulation pump filtrate is circulated between vaporizer and interchanger, pump circulation heating and transpiring moisture, controlled temperature is at 95-97 ℃, after making it to reach supersaturated solution, be sent to and be cooled to 55～60 ℃ of crystallizations in the water cooler, the crystallized mixed slip is sent to whizzer to be separated, after saleratus is separated through oven dry again after carbonization quantitative package get the salt of wormwood product;

4) briquetting charcoal, drying and gather dust: through behind extracting and separating and the filtration washing the charcoal filter cake, its ash oontent reduces greatly, drying is made the powdered carbon product; Also can be pressed into brick fuel, charcoal piece, dry packing.

The present invention is from organic chemical industry's products such as offal, the carbonization of tobacco leaf briquetting, gasification extraction nicotine, eggplant Buddhist nun alcohol, contain 10% potassium oxide in the charcoal, can produce salt of wormwood, vitriolate of tartar, saltpetre, Repone K etc. through water-soluble method or acid pasting, they can be used as agricultural fertilizer, the manufacture salt of wormwood etc. of also can purifying, at last the refining carbon product.Available product has: organic compound such as salt of wormwood, refining carbon, vitriolate of tartar, saltpetre, Repone K, wood gas, nicotine.

Have following characteristics compared with the prior art:

1, raw material difference

Yunnan Province is the main producing region of tobacco, annual produces about 60,000 tons rotten tobacco leaf, redrying offal, confiscates tobacco leaf, confiscates raw material such as pipe tobacco, and raw material of the present invention is different with other production technique use KCI raw material.

2, byproduct difference

Byproduct of the present invention is refining charcoal, and refining charcoal is the raw material of chemical industry, agricultural chemicals, agricultural, daily life, war industry, and this technology does not have waste residue to get rid of.

3, production technique difference

The present invention be adopt dissolving, filter, concentrate, the crystalline method is produced salt of wormwood, refining charcoal, technical process is simple, invests for a short time, the products production cost is low.

Description of drawings

Fig. 1 is the technological process block-diagram of invention.

Embodiment

Embodiment:

1, offal charcoal processing technology

1) broken, dry, gather dust and briquetting: the raw material offal is dried through after the fragmentation, makes water content less than 20%, and drying temperature is controlled at (wood gas that exsiccant fuel can directly use offal briquetting or subsequent technique to produce) below 70 ℃.Hot blast is produced by hotblast stove, emptying after the tail gas process dedusting conformance with standard; The exsiccant offal is collected by tornado dust collector after screw feeder is assigned to briquetting in the briquetting press; At normal temperatures the tobacco stalk raw material of pulverizing is compressed into density at 1g/cm ³About piece material (can satisfy the requirement of carbonization technique);

2) charing, gasification: the offal piece is added into and carries out drying, gasification, charing in the carbonization kiln; Drying temperature in 150 ℃, about about 1 hour of time of drying; When temperature continues to rise, when surpassing 275 ℃, raw material begins to accelerate to decompose, along with temperature raises, decomposition rate is accelerated, generate a large amount of resolvents, as methane, ethane, nicotine etc., under anaerobic conditions also produce simultaneously CO gas, owing to contain oxygen element in the offal, it is thermopositive reaction (need not heat outward reaction is gone on) that this phase table reveals, this phase temperature remains to 400～450 ℃, the product that obtains has charcoal, wood gas, nicotine etc., wherein the output of charcoal is the highest, wood gas output lower (because also having some volatile matters not to be decomposed out in the product charcoal); If make the wood gas quality good, tolerance and calorific value also increase, and pyrolytic process can also continue, and temperature is in 550～600 ℃ of charings, gasification in the control stove; Producing wood gas, mainly is CO, CH4 and H2 wherein, obtains offal charcoal, inflammable gas and part nicotine (the nearly 300kg/ ton of the yield of charcoal offal piece).

3) nicotine recovery of oil and inflammable gas are collected: the inflammable gas (wood gas) that is come out by gasifying type carbide furnace operation reclaims nicotine through overcooling, removes purifying gas behind the detrimental impurity and can make fuel and use.Inflammable gas enters two-stage cooler, being recycled below the water cooling to 70 ℃ (at this moment has phlegma to discharge), enter gas-liquid separator then and remove phlegma, enter the alkali scrubber alkali cleaning again, use the washing lotion wash cycles, remove the impurity in the combustion gas, after blower fan pressurization, purification, be admitted in the gas storage holder, deliver to hotblast stove and respectively use device of air through gas transmission and distribution system through combustion gas after the foam removal.The hot water that water cooler comes out flows into circulating water pool after the water cooling tower cooling, send water cooler back to through water circulating pump again and recycle.

2, the production technique of salt of wormwood (vitriolate of tartar, saltpetre, Repone K), refining charcoal

The main component of the above-mentioned offal charcoal that obtains is: charcoal, salt of wormwood, phosphoric acid salt etc., contain 9-1%K approximately ₂O, it is low more good more generally the composition beyond the carbon removal to be required in industry is used, and the composition beyond the carbon removal is an impurity, foreign matter content is high more, the use range of charcoal is restricted more, and thermal value is also low more, for improving the content of carbon, need further with carbon purifying, improve carbon content, enlarge the use range of charcoal, improve the value of charcoal, reclaim the potassium oxide in the carbon, rationally utilize byproduct.

1) broken and gather dust, powdered carbon slurrying: can select two kinds of technologies for use, the one, directly grinds (liquid phase is from filter and cleaning process), also slurrying simultaneously through the flame-out back of water through wet wheeling machine.The 2nd, flame-out cooling back adds washing water (from filter and cleaning process) slurrying with powdered carbon after the FFC600 crusher in crushing.

With the offal charcoal after the fragmentation under agitation condition with hot water thorough mixing in extraction tank, thereby make salts such as salt of wormwood soluble in water, aqueous solvent can come from follow-up filtration washing water and filtrate, solvent temperature is 80～90 ℃, a large amount of salts such as salt of wormwood are dissolved in the liquid phase, and the control carbon content is at 25-28%;

Above-mentioned also available acid pasting, as: utilize the metallic salt in nitric acid, sulfuric acid, the dissolving with hydrochloric acid charcoal, obtain corresponding metal nitrate, vitriol, hydrochloride.The mol amount summation that the add-on of acid press carbonate in the charcoal, phosphate radical and metal-salt is calculated and is added, with the free acid content in the maintenance slip 2% ± 0.5.The purity of the salt of wormwood that this method obtains will be lower than water-soluble method, because the composition that extracts in the water-soluble method technology is mainly based on the salt of wormwood of solubility, but the more water-soluble method of the charcoal that this method obtains is pure.Its technological process is identical with WATER-WASHING METHOD.Two kinds of technologies can realize in same set of device.

2) charcoal is starched and filtered and washing: the filter cake (filter cake thickness 35-40mm) after the charcoal slurry filters washs three times with the 1.5-2 times of water yield of charcoal amount, water temperature: 80～85 ℃, blot then, the filtrate of once washing liquid turns back to broken dust-precipitator (can select for use belt vacuum filter to separate and washing).

3) filtrate evaporation concentration, crystallisation by cooling, Crystallization Separation, crystallizing and drying: get clear liquid after filtrate is left standstill through insulation and deliver to vaporizer, evaporating required heat can be provided by graphite heat exchanger heating potassium solution by steam, use forced circulation pump that filtrate is circulated between vaporizer and interchanger, pump circulation heating and transpiring moisture, controlled temperature is at 95-97 ℃, after making it to reach supersaturated solution, be sent to and be cooled to 55～60 ℃ of crystallizations in the water cooler, the crystallized mixed slip is sent to whizzer to be separated, after saleratus is separated through oven dry again after carbonization quantitative package get the salt of wormwood product.The isolated mother liquor of whizzer is delivered to shredder and is joined slurry or concentrated.

4) briquetting charcoal, drying and gather dust: the offal charcoal after through extracting and separating and filtration washing the charcoal filter cake, its ash oontent reduces greatly, can select drying to make the powdered carbon product; Also can be pressed into brick fuel, charcoal piece again, the back list marketing of drying packing, the back product ash content of purifying has been widened Application Areas less than 1%, has improved value of the product.

The index analysis such as the following table 4.2 of offal and gasification back gained charcoal

Claims (1)

1. an extracting potassium carbonate from cabo reaches the method made from extra care charcoal, it is characterized in that carrying out according to the following steps:

(1) offal charcoal processing:

1) broken, dry, gather dust and briquetting: the raw material offal is dried through after the fragmentation, and water content is less than 20%, and drying temperature is controlled at below 70 ℃, and tail gas is through emptying after the dedusting; The exsiccant offal is collected back briquetting in the briquetting press;

2) charing, gasification: the offal piece is added into and carries out drying, gasification, charing in the carbonization kiln; Drying temperature in 150 ℃, 1-2 hour time of drying; When temperature continues to rise, when surpassing 275 ℃, raw material begins to accelerate to decompose, along with temperature raises, decomposition rate is accelerated, and generates a large amount of resolvents, methane, ethane, nicotine, simultaneously under anaerobic conditions also produce CO gas, this phase temperature remains to 400～450 ℃, obtains charcoal, wood gas, nicotine product; Temperature is controlled at 550～600 ℃ of charings, obtains the offal charcoal, contains CO, CH ₄And H ₂Wood gas inflammable gas and nicotine;

3) nicotine recovery of oil and inflammable gas are collected: reclaim nicotine, inflammable gas is cooled to below 70 ℃, enters gas-liquid separator then and removes phlegma, enters alkali cleaning again, removes the impurity in the combustion gas, passes through foam removal, pressurizes, sends in the gas storage holder;

(2) preparation of salt of wormwood, refining charcoal:

1) the offal charcoal broken and gather dust, powdered carbon slurrying: with the offal charcoal after the fragmentation under agitation condition with hot water thorough mixing in extraction tank, thereby make salts such as salt of wormwood soluble in water, aqueous solvent comes from follow-up filtration washing water and filtrate, solvent temperature is 80～90 ℃, a large amount of salts such as salt of wormwood are dissolved in the liquid phase, and the control carbon content is at 25-28%;

Perhaps utilize the metallic salt in nitric acid, sulfuric acid, the dissolving with hydrochloric acid charcoal, obtain corresponding metal nitrate, vitriol, hydrochloride, the add-on of acid is pressed the mol amount summation of carbonate in the charcoal, phosphate radical and metal-salt and is calculated adding, and the free acid content in the maintenance slip is 2% ± 0.5;

2) charcoal is starched and filtered and washing: the filter cake after the charcoal slurry filters washs water temperature: 80～85 ℃ three times with the 1.5-2 times of water yield of charcoal amount;

3) filtrate evaporation concentration, crystallisation by cooling, Crystallization Separation, crystallizing and drying: get clear liquid after filtrate is left standstill through insulation and deliver to vaporizer, with forced circulation pump filtrate is circulated between vaporizer and interchanger, pump circulation heating and transpiring moisture, controlled temperature is at 95-97 ℃, after making it to reach supersaturated solution, be sent to and be cooled to 55～60 ℃ of crystallizations in the water cooler, the crystallized mixed slip is sent to whizzer to be separated, after saleratus is separated through oven dry again after carbonization quantitative package get the salt of wormwood product;

4) briquetting charcoal, drying and gather dust: through behind extracting and separating and the filtration washing the charcoal filter cake, its ash oontent reduces greatly, drying is made the powdered carbon product; Be pressed into brick fuel, charcoal piece, dry packing.

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