CN105062604B - Preparation method of high-performance coal briquettes and technology for preparing water gas from coal briquettes - Google Patents

Abstract

The invention discloses a preparation method of high-performance coal briquettes and a technology for preparing water gas from the coal briquettes. A sodium humate composite binder rich in nanometer rare earth is adopted for preparation of the coal briquettes, and the coal briquettes are prepared from relatively cheap slack coal with a special technology. The invention further provides a preparation method and an application of feed gas. The technology for preparing the water gas from the coal briquettes is low in cost, the gas quality is high, and the coal briquettes are wide in application range, are widely applied to synthetic ammonia, methanol, methanol co-production enterprises and the like, can completely replace high-quality pea coal and create high economic benefit and social benefit for the enterprises.

Description

A kind of preparation method of high-performance moulded coal and water-gas technology is produced by the moulded coal

Technical field

The invention belongs to water-gas preparing technical field, and in particular to the preparation method of a kind of high-performance moulded coal and by the type Coal produces water-gas technology.

Background technology

China is little nitrogen big producer, according to the statistics made by the departments concerned, in, little nitrogen, methanol production enterprise there are about more than 800 It is individual, wherein 60% above is traditional static bed gas making, using anthracite block coal as gas making feed coal, needs lump coal about every year 30000000 t.Due to the influence that the raising of mining mechanization degree and coal field geology are constructed, the yield of anthracite block coal is very low.Therefore, The imbalance between supply and demand of anthracite block coal day is becoming tight, it is difficult to ensure the regular supply of enterprise's gas making feed coal, and substantial amounts of anthracite fine coal But it is long-term to overstock because utilization rate is low, cause the waste of resource and the pollution of environment；Meanwhile, chemical fertilizer factory's lump coal, due to Breakage in transportation, has also overstock some fine coal.In the Ammonia Production of chemical fertilizer factory, expense of raw materials accounts for total production cost More than 2/3, so in this case, develop efficiently, the moulded coal of cleaning make and substitute lump coal and produce water-gas technology, Lump coal imbalance between supply and demand can not only be alleviated, coal resources are made full use of, while can also reduce raw materials for production cost, enterprise's warp is improved Ji benefit.

The content of the invention

It is an object of the invention to solve above-mentioned technical problem present in prior art, there is provided a kind of high-performance moulded coal Preparation method and water-gas technology is produced by the moulded coal.

In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：

The preparation method of high-performance moulded coal of the invention, comprises the steps：

（1）With isooctane as solvent, nano rare earth is deployed into the nano rare earth that mass percent concentration is 8 ~ 12% molten Liquid；

（2）It is 5 ~ 15% sodium hydroxide solution that mass percent concentration is added in batch box, and oxygen is hydrogenated with toward batch box is interior While changing sodium solution, the nano rare earth solution for modulating, nano rare earth solution is added to account for mixed liquor gross mass by measuring pump 1.0%；

（3）The weathered coal powder of granularity≤1.2mm is put into dosage bunker, mixing nano rare earth solution is added by measuring pump Sodium hydroxide solution afterwards, controls PH to 10-11, liquid-solid ratio 9:1, extracting tank is sent to after stirring and evenly mixing, jacket steam heating makes Temperature is raised to 85~90 DEG C in tank, and stirring reaction 0.5h, releasing is dried and obtains the sodium humate rich in rare earth；

（4）The sodium humate that will be enriched in rare earth is soluble in water, and the mass percent concentration of the sodium humate rich in rare earth is 5% ~ 15%, with 90 ~ 95 DEG C of liquid temperature degree, constant temperature time 1 ~ 2 hour, to montmorillonite powder and kaolin is added in above-mentioned solution, is rich in The sodium humate of rare earth, montmorillonite powder and kaolinic mass ratio are 4:3:2, mixing obtains compound binding agent；

（5）The feed coal of the composite adhesive that will be prepared and granularity less than 3mm is mixed, compoiste adhering and feed coal Mass ratio be 1:4 ~ 8, stirring after retting 24-28 hours, is dried by drying oven at machine for producing coal bars extruding, 110 DEG C~150 DEG C Obtain coal rod of coal briquette.

Described nano rare earth includes yttrium, cerium, lanthanum compound or salt, and the gross mass of yttrium, cerium, lanthanum compound or salt accounts for nanometer The 70% of rare earth gross mass, single proportion is more than 20%, and remaining component is optional in dysprosium, lutetium, erbium, the compound of europium or salt 1 ~ 3 kind.

Described nano rare earth is preferably the mixing of dysprosium carbonate, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, lanthanum carbonate Thing, the dysprosium carbonate, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, the mass ratio of lanthanum carbonate are 10:12:8: 20:25:25.

Water-gas technology is prepared using moulded coal of the invention, concrete technology is：Moulded coal Belt Conveying to Gas-making Furnace feed bin, Added in Gas-making Furnace through automatic stoker, to blowing air in stove, improve furnace temperature, then passed to vapor and reacted with hot carbon, Qualified water-gas is obtained, Gas-making Furnace upper temp is controlled at 260~300 DEG C；Descending temperature control is at 270~310 DEG C；Water steams 190~210 DEG C of stripping temperature；Single stove enters stove blast≤27KPa；Steam in the boiler pressure is 0.05~0.055MPa.

The water-gas that 280 DEG C of temperature enters waste heat boiler, further reduces water-gas temperature, while byproduct steam, afterwards Water-gas enters aeration tower and further washs cooling, goes out 35 DEG C or so of aeration tower water-gas temperature, enters gas holder buffer storage.

In the present invention, adhesive is formed using the natural weathered coal containing humic acid through chemistry refinement, during making Add various nanoparticle rare earths, form multi-functional macromolecular compound, containing hydroxyl, quinonyl, the more activity such as carboxyl Group, with very big internal surface area, there is stronger absorption, exchanges, complexing, sequestering power, its effect mainly enhancing moulded coal Intensity.

Nanoparticle has very strong chemism, and this is that, because its surface area is big, surface can be high, and nano-particle surface contains There are many functional groups, surface atom number increases and surface atom coordination is unsaturated, forms substantial amounts of dangling bonds and unsaturated bond, this Plant dangling bonds and unsaturated bond causes that nanoparticle has surface-active high（Surface energy）, this is advantageous for chemical reaction. The burning of combustion gas is belonging to a kind of oxidation --- reduction reaction, so nano rare earth particulate can promote burning, be conducive to gas making to exist High temperature required for manufacture water-gas, temperature is higher, and active ingredient will be higher in water-gas.This nano rare earth is added to add Agent, can more promote the burning completely of fuel.In sum, the present invention adds nano rare earth catalytic combustion-supporting, heat in raw material making Efficiency will be greatly improved.

In addition sodium humate and montmorillonite and kaolinic hybrid adhesive are used, montmorillonite and kaolin can be significantly improved The high-temperature behavior of moulded coal, and kaolin can improve the ash fusibility of moulded coal.Montmorillonite and kaolin are belonged to by mineralogical composition Clay, clay is crystalline solid, belongs to phyllosilicate, and main composition is the extremely tiny clay mineral of particle, after being spontaneously wet out by water There is good plasticity and caking property, hardened after drying, be favorably improved the normal temperature strength of moulded coal；In temperature-rise period, clay Occur that dehydration, volumetric expansion and contraction etc. change, the plasticity of clay disappears after adsorbed film of water loses in clay, but by Effect is attached to each other so that moulded coal product still has good intensity in high temperature when particle is in close contact；There are mineral in clay The temperature of decomposition is all very high, and this also causes that the moulded coal product using clay as binding agent has good heat endurance, and this is rotten The birth defects of the organic briquette binder of sodium phytate.Moulded coal is except that need to meet the basic demands such as mechanical strength and heat endurance Outward, in addition it is also necessary to have and ash fusibility higher and be difficult the performances such as clinkering property, this normal operation to the working of a furnace, ventilation and deslagging in stove All it is of great benefit to Deng operation, especially on gasification briquette, kaolinic addition can improve the ash fusibility of moulded coal.

The beneficial effects of the present invention are：

（1）The need for meeting industry to patch fuel；

（2）Rationally utilize inferior fuel；

（3）Poorly efficient raw coal is converted into high efficient energy sources, coal-saving environmental protection；

（4）The raw coal of non-clean burning is converted into clean fuel；

（5）Small investment, low cost is practical, will produce huge economic benefit and good social benefit.

Brief description of the drawings

Fig. 1 is the process chart of moulded coal preparation in the present invention.

Fig. 2 is the process chart of water-gas preparation in the present invention.

Specific embodiment

With reference to specific embodiment, the present invention is further illustrated.

（One）The selection of feed coal：The main feed coal that raw material foam coal is manufactured as moulded coal, its fine or not direct relation To the quality of moulded coal, and then tolerance processed, the gas componant of gas making are had influence on, directly influence yield and the consumption of subsequent production, So, the selection of raw material foam coal property is very vital.

According to the physics and chemical property of gas-making coal, anthracite is the fabulous raw material of gas-making type coal processed.Jincheng, Shanxi Province coal The coal in field belongs to low ash, low-sulfur, the coal of golf calorific value, is the optimum feed stock coal for manufacturing moulded coal, the moulded coal sulphur made with it is low, Fixed carbon is high, cold strength and calorific intensity are high, so Gas-making Furnace system is large-minded, makings is excellent, is well suited as the original of production of shaped coal Material.Therefore, the coal in Jincheng, Shanxi Province coalfield is selected in the present invention as feed coal.

Performance indications and detection method：

（1）Normal temperature strength：To be taken out from drying box after moulded coal sample drying, be cooled to room temperature, instrument is examined with hydraulic pressure strength Its compression strength is surveyed, in this, as moulded coal normal temperature strength.

（2）Elevated temperature strength：First moulded coal sample is put into the can with cover equipped with sand, moulded coal sample is covered with sand, Then can with cover is put into after being incubated 0.5h in 850 DEG C of Muffle furnace and is taken out, measure its compression strength at high temperature immediately, In this, as moulded coal elevated temperature strength.

（3）Heat endurance.First moulded coal sample is put into the can with cover equipped with sand, moulded coal sample is covered with sand, Then can with cover is put into 850 DEG C of Muffle furnace after being incubated 30 min and is taken out, after being cooled to room temperature, be put into vibration screening machine vibrations After 2min, 13mm sieves are crossed, take moulded coal of the size more than 13mm and account for the quality percentage of total amount as heat endurance index.

Embodiment 1

1st, the preparation method of moulded coal

（1）With isooctane as solvent, nano rare earth is deployed into the nano rare earth solution that mass percent concentration is 8%；Institute The mixture of the nano rare earth stated preferably dysprosium carbonate, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, lanthanum carbonate, the carbonic acid Dysprosium, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, the mass ratio of lanthanum carbonate are 10:12:8: 20:25:25.

（2）The sodium hydroxide solution that mass percent concentration is 5% is added in batch box, toward the interior hydrogenation oxidation of batch box While sodium solution, the nano rare earth solution for modulating, nano rare earth solution is added to account for mixed liquor gross mass by measuring pump 1.0%。

（3）The weathered coal powder of granularity≤1.2mm is put into dosage bunker, mixing nano rare earth solution is added by measuring pump Sodium hydroxide solution afterwards, controls PH to 10-11, liquid-solid ratio 9:1, extracting tank is sent to after stirring and evenly mixing, jacket steam heating makes Temperature is raised to 85 DEG C in tank, and stirring reaction 0.5h, releasing is dried and obtains the sodium humate rich in rare earth.

（4）The sodium humate that will be enriched in rare earth is soluble in water, and the mass percent concentration of the sodium humate rich in rare earth is 5%, with 90 ~ 95 DEG C of liquid temperature degree, constant temperature time 1 ~ 2 hour, to montmorillonite powder and kaolin is added in above-mentioned solution, rich in rare earth Sodium humate, montmorillonite powder and kaolinic mass ratio be 4:3:2, mixing obtains compound binding agent.

（5）The feed coal of the composite adhesive that will be prepared and granularity less than 3mm is mixed, compoiste adhering and feed coal Mass ratio be 1:4, stirring, retting obtains type after 28 hours by drying oven drying at machine for producing coal bars extruding, 110 DEG C~115 DEG C Coal coal rod.

Coal rod normal temperature strength is 1.2 MPa；Elevated temperature strength is 1.0 MPa, and heat endurance is 88%.

2nd, water-gas technology is prepared

Moulded coal Belt Conveying to Gas-making Furnace feed bin, adds in Gas-making Furnace through automatic stoker, to blowing air in stove, improves Furnace temperature, then passes to vapor and the reaction of hot carbon, is obtained qualified water-gas, the control of Gas-making Furnace upper temp 260~ 270℃；Descending temperature control is at 270~280 DEG C；190~200 DEG C of steam temperature；Single stove enters stove blast≤27KPa；Enter stove Vapour pressure is 0.05~0.055MPa.

The water-gas that 280 DEG C of temperature enters waste heat boiler, further reduces water-gas temperature, while byproduct steam, afterwards Water-gas enters aeration tower and further washs cooling, goes out 35 DEG C or so of aeration tower water-gas temperature, enters gas holder buffer storage.

Embodiment 2

1st, the preparation method of moulded coal

（1）With isooctane as solvent, nano rare earth is deployed into the nano rare earth solution that mass percent concentration is 12%； Described nano rare earth is preferably the mixture of dysprosium carbonate, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, lanthanum carbonate, the carbon Sour dysprosium, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, the mass ratio of lanthanum carbonate are 10:12:8: 20:25:25.

（2）The sodium hydroxide solution that mass percent concentration is 10% is added in batch box, toward the interior hydrogenation oxidation of batch box While sodium solution, the nano rare earth solution for modulating, nano rare earth solution is added to account for mixed liquor gross mass by measuring pump 1.0%；

（3）The weathered coal powder of granularity≤1.2mm is put into dosage bunker, mixing nano rare earth solution is added by measuring pump Sodium hydroxide solution afterwards, controls PH to 10-11, liquid-solid ratio 9:1, extracting tank is sent to after stirring and evenly mixing, jacket steam heating makes Temperature is raised to 90 DEG C in tank, and stirring reaction 0.5h, releasing is dried and obtains the sodium humate rich in rare earth；

（4）The sodium humate that will be enriched in rare earth is soluble in water, and the mass percent concentration of the sodium humate rich in rare earth is 15%, with 90 ~ 95 DEG C of liquid temperature degree, constant temperature time 1 ~ 2 hour, to montmorillonite powder and kaolin is added in above-mentioned solution, rich in rare earth Sodium humate, montmorillonite powder and kaolinic mass ratio be 4:3:2, mixing obtains compound binding agent.

（5）The feed coal of the composite adhesive that will be prepared and granularity less than 3mm is mixed, compoiste adhering and feed coal Mass ratio be 1:5, stirring, retting obtains type after 28 hours by drying oven drying at machine for producing coal bars extruding, 140 DEG C~150 DEG C Coal coal rod.

2nd, water-gas technology is prepared

Moulded coal Belt Conveying to Gas-making Furnace feed bin, adds in Gas-making Furnace through automatic stoker, to blowing air in stove, improves Furnace temperature, then passes to vapor and the reaction of hot carbon, is obtained qualified water-gas, the control of Gas-making Furnace upper temp 290~ 300℃；Descending temperature control is at 300~310 DEG C；200~210 DEG C of steam temperature；Single stove enters stove blast≤27KPa；Enter stove Vapour pressure is 0.05~0.055MPa.

The water-gas that 280 DEG C of temperature enters waste heat boiler, further reduces water-gas temperature, while byproduct steam, afterwards Water-gas enters aeration tower and further washs cooling, goes out 35 DEG C or so of aeration tower water-gas temperature, enters gas holder buffer storage.

Embodiment 3

1st, the preparation method of moulded coal

（1）With isooctane as solvent, nano rare earth is deployed into the nano rare earth solution that mass percent concentration is 10；Institute The nano rare earth stated is dysprosium carbonate, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, the mixture of lanthanum carbonate, the dysprosium carbonate, nitre Sour lutetium, erbium chloride, yttrium fluoride, cerium oxide, the mass ratio of lanthanum carbonate are 12:10:8: 25:25:20.

（2）The sodium hydroxide solution that mass percent concentration is 15% is added in batch box, toward the interior hydrogenation oxidation of batch box While sodium solution, the nano rare earth solution for modulating, nano rare earth solution is added to account for mixed liquor gross mass by measuring pump 1.0%；

（3）The weathered coal powder of granularity≤1.2mm is put into dosage bunker, mixing nano rare earth solution is added by measuring pump Sodium hydroxide solution afterwards, controls PH to 10-11, liquid-solid ratio 9:1, extracting tank is sent to after stirring and evenly mixing, jacket steam heating makes Temperature is raised to 87 DEG C in tank, and stirring reaction 0.5h, releasing is dried and obtains the sodium humate rich in rare earth；

（4）The sodium humate that will be enriched in rare earth is soluble in water, and the mass percent concentration of the sodium humate rich in rare earth is 10%, with 90 ~ 95 DEG C of liquid temperature degree, constant temperature time 1 ~ 2 hour, to montmorillonite powder and kaolin is added in above-mentioned solution, rich in rare earth Sodium humate, montmorillonite powder and kaolinic mass ratio be 4:3:2, mixing obtains compound binding agent.

（5）The feed coal of the composite adhesive that will be prepared and granularity less than 3mm is mixed, compoiste adhering and feed coal Mass ratio be 1:8, stirring, retting obtains type after 26 hours by drying oven drying at machine for producing coal bars extruding, 120 DEG C~125 DEG C Coal coal rod.

2nd, water-gas technology is prepared

Moulded coal Belt Conveying to Gas-making Furnace feed bin, adds in Gas-making Furnace through automatic stoker, to blowing air in stove, improves Furnace temperature, then passes to vapor and the reaction of hot carbon, is obtained qualified water-gas, the control of Gas-making Furnace upper temp 270~ 280℃；Descending temperature control is at 290~300 DEG C；200~205 DEG C of steam temperature；Single stove enters stove blast≤27KPa；Enter stove Vapour pressure is 0.05~0.055MPa.

The water-gas that 280 DEG C of temperature enters waste heat boiler, further reduces water-gas temperature, while byproduct steam, afterwards Water-gas enters aeration tower and further washs cooling, goes out 35 DEG C or so of aeration tower water-gas temperature, enters gas holder buffer storage.

Embodiment 4

1st, the preparation method of moulded coal

（1）With isooctane as solvent, nano rare earth is deployed into the nano rare earth solution that mass percent concentration is 9%；Institute The nano rare earth stated is dysprosium carbonate, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, the mixture of lanthanum carbonate, the dysprosium carbonate, nitre Sour lutetium, erbium chloride, yttrium fluoride, cerium oxide, the mass ratio of lanthanum carbonate are 12:10:8: 25:22:23.

（2）The sodium hydroxide solution that mass percent concentration is 12% is added in batch box, toward the interior hydrogenation oxidation of batch box While sodium solution, the nano rare earth solution for modulating, nano rare earth solution is added to account for mixed liquor gross mass by measuring pump 1.0%；

（3）The weathered coal powder of granularity≤1.2mm is put into dosage bunker, mixing nano rare earth solution is added by measuring pump Sodium hydroxide solution afterwards, controls PH to 10-11, liquid-solid ratio 9:1, extracting tank is sent to after stirring and evenly mixing, jacket steam heating makes Temperature is raised to 88 DEG C in tank, and stirring reaction 0.5h, releasing is dried and obtains the sodium humate rich in rare earth；

（4）The sodium humate that will be enriched in rare earth is soluble in water, and the mass percent concentration of the sodium humate rich in rare earth is 6%, with 90 ~ 95 DEG C of liquid temperature degree, constant temperature time 1 ~ 2 hour, to montmorillonite powder and kaolin is added in above-mentioned solution, rich in rare earth Sodium humate, montmorillonite powder and kaolinic mass ratio be 4:3:2, mixing obtains compound binding agent.

（5）The feed coal of the composite adhesive that will be prepared and granularity less than 3mm is mixed, compoiste adhering and feed coal Mass ratio be 1:6, stirring, retting obtains type after 27 hours by drying oven drying at machine for producing coal bars extruding, 125 DEG C~130 DEG C Coal coal rod.

2nd, water-gas technology is prepared

Moulded coal Belt Conveying to Gas-making Furnace feed bin, adds in Gas-making Furnace through automatic stoker, to blowing air in stove, improves Furnace temperature, then passes to vapor and the reaction of hot carbon, is obtained qualified water-gas, the control of Gas-making Furnace upper temp 290~ 295℃；Descending temperature control is at 300~305 DEG C；190~210 DEG C of steam temperature；Single stove enters stove blast≤27KPa；Enter stove Vapour pressure is 0.05~0.055MPa.

The water-gas that 280 DEG C of temperature enters waste heat boiler, further reduces water-gas temperature, while byproduct steam, afterwards Water-gas enters aeration tower and further washs cooling, goes out 35 DEG C or so of aeration tower water-gas temperature, enters gas holder buffer storage.

Claims (4)

1. a kind of preparation method of high-performance moulded coal, it is characterised in that comprise the steps：

（1）With isooctane as solvent, nano rare earth is deployed into the nano rare earth solution that mass percent concentration is 8 ~ 12%；

（2）It is 5 ~ 15% sodium hydroxide solution that mass percent concentration is added in batch box, and oxidation is hydrogenated with toward batch box is interior While sodium solution, the nano rare earth solution for modulating, nano rare earth solution is added to account for mixed liquor gross mass by measuring pump 1.0% ；

（3）The weathered coal powder of granularity≤1.2mm is put into dosage bunker, after measuring pump adds mixing nano rare earth solution Sodium hydroxide solution, control PH to 10-11, liquid-solid ratio 9:1, extracting tank is sent to after stirring and evenly mixing, jacket steam heating makes Temperature is raised to 85~90 DEG C in tank, and stirring reaction 0.5h, releasing is dried and obtains the sodium humate rich in rare earth；

（4）The sodium humate that will be enriched in rare earth is soluble in water, the mass percent concentration of the sodium humate rich in rare earth for 5% ~ 15%, with 90 ~ 95 DEG C of liquid temperature degree, constant temperature time 1 ~ 2 hour, to montmorillonite powder and kaolin is added in above-mentioned solution, rich in dilute The sodium humate of soil, montmorillonite powder and kaolinic mass ratio are 4:3:2, mixing obtains compound binding agent；

（5）The feed coal of the composite adhesive that will be prepared and granularity less than 3mm is mixed, compoiste adhering and feed coal Mass ratio is 1:4 ~ 8, stirring after retting 24-28 hours, is dried by drying oven at machine for producing coal bars extruding, 110 DEG C~150 DEG C Obtain coal rod of coal briquette.

2. the preparation method of the high-performance moulded coal according to claim 1, it is characterised in that：Described nano rare earth includes Yttrium, cerium, lanthanum compound or salt, the gross mass of yttrium, cerium, lanthanum compound or salt account for the 70% of nano rare earth gross mass, shared by single Ratio is more than 20%, and remaining component is optional 1 ~ 3 kind in dysprosium, lutetium, erbium, the compound of europium or salt.

3. the preparation method of the high-performance moulded coal according to claim 2, it is characterised in that：Described nano rare earth is carbon Sour dysprosium, lutecium nitrate, erbium chloride, yttrium fluoride, cerium oxide, the mixture of lanthanum carbonate, the dysprosium carbonate, lutecium nitrate, erbium chloride, fluorination Yttrium, cerium oxide, the mass ratio of lanthanum carbonate are 10:12:8: 20:25:25.

4. water-gas method is prepared using the described high-performance moulded coals of one of claim 1-3, it is characterised in that：Coal rod of coal briquette With Belt Conveying to Gas-making Furnace feed bin, added in Gas-making Furnace through automatic stoker, to blowing air in stove, improve furnace temperature, Ran Houtong Enter vapor to be reacted with hot carbon, qualified water-gas is obtained, Gas-making Furnace upper temp is controlled at 260~300 DEG C；Under Trip temperature is controlled at 270~310 DEG C；190~210 DEG C of steam temperature；Single stove enters stove blast≤27KPa；Enter stove steaming Vapour pressure is 0.05~0.055MPa.