CN104828824A - A method of preparing calcium carbide by co-molding of carbide slag and coke powder - Google Patents
A method of preparing calcium carbide by co-molding of carbide slag and coke powder Download PDFInfo
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- CN104828824A CN104828824A CN201510129164.9A CN201510129164A CN104828824A CN 104828824 A CN104828824 A CN 104828824A CN 201510129164 A CN201510129164 A CN 201510129164A CN 104828824 A CN104828824 A CN 104828824A
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- slag
- carbide
- calcium carbide
- coke powder
- ball
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- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000005997 Calcium carbide Substances 0.000 title claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002893 slag Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000013037 co-molding Methods 0.000 title abstract 3
- 238000001354 calcination Methods 0.000 claims abstract description 43
- 239000000292 calcium oxide Substances 0.000 claims abstract description 32
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000011280 coal tar Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 241000772415 Neovison vison Species 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 52
- 235000012255 calcium oxide Nutrition 0.000 abstract description 31
- 239000008188 pellet Substances 0.000 abstract description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 2
- SBLCGFVUYJGJIS-UHFFFAOYSA-N [O-2].[Ca+2].[C+4].[O-2].[O-2] Chemical compound [O-2].[Ca+2].[C+4].[O-2].[O-2] SBLCGFVUYJGJIS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000920 calcium hydroxide Substances 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 238000005453 pelletization Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 9
- 235000011941 Tilia x europaea Nutrition 0.000 description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 9
- 239000000571 coke Substances 0.000 description 9
- 239000004571 lime Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method of preparing calcium carbide by co-molding of carbide slag (Ca(OH)2) and coke powder (biochar and semicoke). The method includes preparing carbon-containing carbide slag (green pellets) by co-molding of purified and modified carbide slag and the coke powder by adoption of an organic binder, calcinating, dehydrating, solidifying to prepare carbon-containing block CaO (processed pellets), and preparing the calcium oxide carbon-containing pellets heat intensity of which at 1000 DEG C is higher than 3 MPa into the calcium carbide in an electric furnace at 1800-1900 DEG C.
Description
Technical field
The present invention is the chemical production technical using organic binder bond calcium carbide to be prepared by carbide slag and coke powder mixing coforming.
Background technology
Calcium carbide produces the important industrial chemicals of acetylene, along with the development of PVC industry, calcium carbide base PVC accounts for ultimate production about 70%, and calcium carbide output constantly increases in recent years, and within 2013, its output reaches 2,234 ten thousand tons.The industrial main method preparing calcium carbide is electric heating process at present: with block calcium oxide and block coke for raw material, utilizes electrothermal oven to heat mixing raw material to 2000-2200 DEG C, generates molten state calcium carbide, its reaction formula 3C+CaO=CaC through a few hours
2+ CO.There is following shortcoming in this technique: 1, the preparation of raw material lump lime needs to calcine a large amount of fat lime stone (high-purity C aCO
3); 2, coke price is expensive, and in coke clamp dog process, produce a considerable amount of coke powder (blue powdered carbon) that cannot directly use, and raw materials cost is high; 3, this calcium carbide preparation process is solid phase thermo-negative reaction, and two reactants are bulk, and reaction area is little, makes raw material mass transfer, heat transfer efficiency low, causes energy consumption higher.
Often use 1 ton of calcium carbide, produce butt carbide slag 1.2 tons, the annual carbide slag output of China is more than 1,800 ten thousand tons, and its main component is calcium hydroxide (Ca (OH)
2).The stacking of a large amount of carbide slag, not only land occupation, but also contaminate environment.Current carbide slag mainly for the production of material of construction such as cement, and for the production of general chemical products such as unslaked lime and prepare the high-end products such as nano-calcium carbonate.
The present invention proposes and a kind ofly add organic matter binding agent strengthening carbide slag and coke powder coforming prepares the method for calcium carbide, according to the requirement of furnace of calcium carbide to block material, the especially requirement of block material purity, activity and hot strength.Emphasis of the present invention solves the purity that carbide slag and coke powder coforming prepare calcium carbide, activity and hot strength, by adding organic binder bond and calcining process, decreasing purity and follow-up energy consumption problem that mineral binder bond brings, improve the purity of shaping rear block of material, activity and hot strength.By the utilization of carbide slag and coke powder, achieve carbide slag and dissolve in a large number and a large amount of recycles of CaO.The hot strength and the activity that wherein improve block material are characteristics and innovation of the present invention points simultaneously.
Beijing Shen Wu energy environment Science and Technology Ltd. develops a series of coal dust and CaO copyrolysis of utilizing and prepares the coke containing CaO, [201310728118.1] invention proposes and mixture is carried out forming processes, obtain block semicoke, obtain high heating value synthesis gas, tar and pyrolysis solid product simultaneously, wherein, described pyrolysis solid product contains coke, semicoke and unslaked lime, the solid product of pyrolysis simultaneously inputs in electric arc furnace when temperature is not less than 450 DEG C, to carry out metallurgy in electric arc furnace, and to obtain calcium carbide.Due to the use of coal dust, particularly in order to tar will be prepared, cause the hot strength completely dissolve containing CaO coke.And instant invention overcomes the problem of block material undercapacity, maintain grog intensity at normal temperatures simultaneously, and then maintain ripe ball hot strength at high temperature, utilize the distinctive wettability of organic binder bond and coke powder, and the hot strength after hot setting, increase substantially hot strength and the furnace-mixing rate of ripe ball.
In addition, a kind of CaO mixes, prepares calcium carbide method [88100821.4] with carbonaceous material has been invented by Chongqing Architectural Engineering College, in order to improve the intensity of ripe ball, its firing temperature is higher, at about 1200 DEG C, although ripe ball hot strength improves, because CaO high temperature sintering is to its active decline rapidly.And the present invention is in order to improve ripe ball hot strength, do not affect ripe ball active, propose the method utilizing purify rear carbide slag and blue powdered carbon coforming, prepare high-heat strength and highly active carbon containing CaO pelletizing, sintering temperature is lower, and ripe ball activity is higher, and its reason forms water vapor after being carbide slag calcining, water vapor has activated coke powder on the one hand, inhibits the sintering of CaO on the one hand.[93112800.5] invented a kind of method that carbide slag prepares carbonized coke ball, in order to increase CaO and coke powder shaping after intensity, although the method is coated on carbon containing CaO pellet generate one deck CaCO
3but at the calcium carbide production temperature of about 2000 DEG C, its hot strength still declines rapidly, because the decomposition temperature of calcium carbonate is 850 degree, therefore the hot strength of this carbonized coke ball still cannot ensure, calcium carbonate enters the heat that furnace of calcium carbide also can consume a part of electric furnace in addition.[2009103110608.3] a kind of method that calcium carbide block material prepared by white lime and coke powder has been invented, although the method also has shaping and stoving process, but its intensity entering stokehold block material still cannot meet the requirement of furnace of calcium carbide, especially stoving process at 500 DEG C, be actually and change white lime into CaO, and this patent does not mention the intensity of CaO and coke powder, applicant's previous experiments shows CaO easy aquation in atmosphere, causes carbon containing CaO pellet strength to disappear.Therefore compared with above mentioned several patent of invention, the present invention has salient feature: (1) utilizes organic binder bond to improve the cold strength of ripe ball, by calcining rear further raising organic binder bond hot strength at high temperature.(2) utilize carbide slag and coke powder, make full use of calcium carbide enterprise existing resource, realize discharge that is energy-conservation and minimizing solid waste.(3) coke powder and CaO can be activated by low temperature calcination, improve coke powder active, and prevent the sintering of CaO from causing activity decrease.
Summary of the invention
The technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, provides a kind of carbide slag (Ca (OH)
2) and coke powder (biological Jiao, blue charcoal) coforming prepare the method for calcium carbide, will to purify and the calcium carbide ground-slag of modification and coke powder organic binder bond coforming prepare carbon containing carbide slag (green-ball), the block CaO (ripe ball) of carbon containing is prepared again through calcined dehydration solidification, the hot strength of this calcium oxide carbonaceous pelletizing at 1000 DEG C is greater than 3MPa, in 1800-1900 DEG C of electric furnace, prepare calcium carbide.
The technology of the present invention solution: modification is carried out to the calcium carbide ground-slag of purifying, and by modified calcium carbide ground-slag, coke powder and organic binder bond and the abundant mix and blend of water, the balling-up agglomerate that then pressurizes prepares carbon containing carbide slag-green-ball; First green-ball controls through oxidation drying, then carries out calcining control acquisition CaO carbonaceous pelletizing-ripe ball, and calcining after-ripening ball is substituted conventional block material, for the production of calcium carbide.
Properties-correcting agent for calcium carbide ground-slag adopts acid or acid salt; Described acid is selected from by one or both in hydrochloric acid, nitric acid, phosphoric acid, acetic acid, sulfuric acid, and described acid salt is selected from by NaHSO
4, NaH
2pO
4, NaHSO
3, Ca (H
2pO
4)
2, Na
2hPO
4, CaHPO
4, Ca
3(PO
4)
2in one or both.
The consumption of described acid or acid salt is 0.5 ~ 3% of calcium carbide ground-slag total mass.
Described carbide slag powder and coke powder need grind and sieve, and its granularity is less than 3mm, is preferably less than 1mm.
Two or more combination formed in starch, Mierocrystalline cellulose, coal tar, mink cell focus, cracked oil, coking coal, pitch class, rubber-like, resol class and organic acid elected as by described organic binder bond, and in binding agent, the mass ratio of each component is 1:1.
The percent mass ratio of described modified carbide slag powder, coke powder, machine binding agent and water: modified carbide slag: coke powder: organic binder bond: water=10:(2.5-5): (1-3): (0.5-2.5), the addition of organic binder bond is the 5%-30% of calcium carbide ground-slag and coke powder gross weight, is optimized for 10%-15%; The addition of water is the 3%-20% of calcium carbide ground-slag and coke powder gross weight, is preferably 5%-15%.
Described moulding pressure 20 ~ 50MPa, is preferably 35 ~ 50MPa.
Described drying control is: under oxygen atmosphere, is heated to 80 ~ 180 DEG C with 20 DEG C/min temperature rise rate, and freeze-day with constant temperature 120 minutes, temperature is preferably 100-150 DEG C.
Described calcining control is: by dried green-ball 500-700 DEG C of scope calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 800 ~ 1000 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
The present invention's advantage is compared with prior art: present invention process is simple, and raw materials used carbide slag, coke powder are the industry byproduct of calcium carbide, chemical industry or smelter, both turn waste into wealth, and again save production cost.Because the mixing between powder raw material, to cold pressing, add the reaction contact surface between raw material, be beneficial to mass transfer, heat transfer, reduce temperature of reaction; Due to high temperature (at the 1000 DEG C) hot strength that calcium oxide carbonaceous pelletizing obtained under different organic matter binding agent and different process calcinating system possesses, increase substantially ripe ball and enter electric furnace ratio, strengthening calcium carbide generation theorem condition, can calcium carbide be generated at 1800-1900 DEG C, realize the energy-conservation of calcium carbide production process.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention;
Fig. 2 is the green-ball prepared after carbide slag and powdered coke shaping;
Fig. 3 is that binding agent and technique are on the impact of hot strength at carbon containing calcium oxide pelletizing 1000 DEG C;
Fig. 4 is the calcium carbide XRD analysis utilizing carbon containing calcium oxide pelletizing to prepare.
Embodiment:
The invention provides a kind of method utilizing carbide slag and coke powder coforming to prepare calcium carbide.The method be first by purify after carbide slag carry out modification, then the organic binder bond of modified calcium carbide ground-slag, coke powder, suitable proportion and a small amount of water are mixed and extrusion forming at normal temperatures, dry through low-temperature oxidation again, obtain dry carbon containing carbide slag pelletizing, then calcined obtained calcium oxide carbonaceous pelletizing.Finally calcium oxide carbonaceous pelletizing is prepared calcium carbide as in electric furnace, its calcium carbide preparation flow is shown in Fig. 1.Fig. 2 is the carbide slag carbonaceous pelletizing obtained in preparation process.Fig. 3 is high temperature (at the 1000 DEG C) hot strength of calcium oxide carbonaceous pelletizing obtained under different binding agent and different process calcinating system.Fig. 4 is the XRD analysis of the calcium carbide that calcium oxide carbonaceous pelletizing that the hot strength wherein at a kind of 1000 DEG C is greater than 3MPa is prepared 1700 DEG C time.
The present invention is introduced in detail below in conjunction with drawings and the specific embodiments.But following embodiment is only limitted to explain the present invention, and protection scope of the present invention should comprise the full content of claim, is not limited only to the present embodiment.
Embodiment 1
By the carbide slag (Ca (OH) after physics removal of impurities
2purity is greater than 95%) pulverize, sieve, divide with sieve focusing dressing sieve, make the granularity of two raw materials be 0.2mm.
In the calcium carbide ground-slag of above-mentioned granularity, add the acetic acid of 1.5%, fully stir, then prepare burden with the mass ratio of coke powder according to 4:1, then add the treated starch of 20% and the water of 6% that account for mixture weight ratio respectively, stir.
The material of mixing is placed on coldmoulding in embedding model machine (forming pressure is 45MPa), obtain the cylinder green-ball of 30g, the cold strength of green-ball is greater than 10MPa.Being placed on by this green-ball is connected with in the loft drier of oxygen, is heated to 100 DEG C with 20 DEG C/min temperature rise rate, freeze-day with constant temperature 120 minutes.
Dried green-ball is placed in retort furnace and is warming up to 550 DEG C of calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 950 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
By the pelletizing block (ripe ball) after calcining at N
2under atmosphere and 1000 DEG C of constant temperature 5 minutes, recording high temperature hot strength was 2.81MPa (in Fig. 3 second sample).
Ripe ball is cooled to about 100 DEG C, then is dropped in electric furnace, 1800 DEG C time, react 40 minutes, obtain calcium carbide, as Fig. 4 analysis.
Embodiment 2
White lime is pulverized, sieves, divide with sieve focusing dressing sieve, make the granularity of two raw materials be 0.2mm.Ca (the H of 1.5% is added in the white lime of above-mentioned granularity
2pO
4)
2, fully stir, then prepare burden with the mass ratio of coke powder according to 7:3, then add and account for the treated starch of mixture weight ratio 20% and the water of 6% respectively, stir.
The material of mixing is placed on coldmoulding in embedding model machine (forming pressure is 45MPa), obtains the cylinder green-ball of 30g.Being placed on by this green-ball is connected with in the loft drier of oxygen, is heated to 120 DEG C with 20 DEG C/min temperature rise rate, freeze-day with constant temperature 120 minutes.
Dried green-ball is placed in retort furnace and is warming up to 600 DEG C of calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 1000 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
By the pelletizing block (ripe ball) after calcining at N
2under atmosphere and 1000 DEG C of constant temperature 5 minutes, recording high temperature hot strength was 4.92MPa (in Fig. 3 the 4th sample).
Ripe ball is cooled to about 100 DEG C, then is dropped in furnace of calcium carbide, 1900 DEG C time, react 40 minutes, obtain calcium carbide, as Fig. 4 analysis.
Embodiment 3
By the carbide slag (Ca (OH) after physics removal of impurities
2purity is greater than 95%) pulverize, sieve, divide with sieve focusing dressing sieve, make the granularity of two raw materials be 0.15mm.
The acetic acid of 1.5% is added in the calcium carbide ground-slag of above-mentioned granularity, abundant stirring, then prepare burden with the mass ratio of coke powder according to 7:3, then add the ethene coal tar, coal tar and the coal-tar pitch that account for mixture weight ratio 10% and the water accounting for mixture weight ratio 5%, stir.
The material of mixing is placed on coldmoulding in embedding model machine (forming pressure is 45MPa), obtains the cylinder green-ball of 30g.Being placed on by this green-ball is connected with in the loft drier of oxygen, is heated to 100 DEG C with 20 DEG C/min temperature rise rate, freeze-day with constant temperature 120 minutes.
Dried green-ball is placed in retort furnace and is warming up to 550 DEG C of calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 950 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
By the pelletizing block (ripe ball) after calcining at N
2under atmosphere and 1000 DEG C of constant temperature 5 minutes, recording high temperature hot strength was 2.72MPa (in Fig. 3 the 9th sample).
Ripe ball is cooled to about 100 DEG C, then is dropped in furnace of calcium carbide, 1900 DEG C time, react 40 minutes, obtain calcium carbide (Fig. 4 analysis).
Embodiment 4
White lime is pulverized, sieves, divide with sieve focusing dressing sieve, make the granularity of two raw materials be 0.2mm.
The phosphoric acid of 1.5% is added in the white lime of above-mentioned granularity, abundant stirring, then prepare burden with the mass ratio of coke powder according to 2:1, then add the ethene coal tar, coal tar and the coal-tar pitch that account for mixture weight ratio 10% and the water accounting for mixture weight ratio 5%, stir.
The material of mixing is placed on coldmoulding in embedding model machine (forming pressure is 45MPa), obtains the cylinder green-ball of 30g.Being placed on by this green-ball is connected with in the loft drier of oxygen, is heated to 150 DEG C with 20 DEG C/min temperature rise rate, freeze-day with constant temperature 120 minutes.
Dried green-ball is placed in retort furnace and is warming up to 600 DEG C of calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 1000 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
By the pelletizing block (ripe ball) after calcining at N
2under atmosphere and 1000 DEG C of constant temperature 5 minutes, recording high temperature hot strength was 2.73MPa (in Fig. 3 the 10th sample).
Ripe ball is cooled to about 100 DEG C, then is dropped in furnace of calcium carbide, 1800 DEG C time, react 40 minutes, obtain calcium carbide (as Fig. 4 analysis).
Embodiment 5
By the carbide slag (Ca (OH) after physics removal of impurities
2purity is greater than 95%) pulverize, sieve, divide with sieve focusing dressing sieve, make the granularity of two raw materials be 0.15mm.
In the calcium carbide ground-slag of above-mentioned granularity, add the phosphoric acid of 1.5%, fully stir, then prepare burden with the mass ratio of coke powder according to 7:3, then add the water of the treated starch 12% accounting for mixture weight ratio 15% respectively, stir.
The material of mixing is placed on coldmoulding in embedding model machine (forming pressure is 45MPa), obtains the cylinder green-ball of 30g.Being placed on by this green-ball is connected with in the loft drier of oxygen, is heated to 120 DEG C with 20 DEG C/min temperature rise rate, freeze-day with constant temperature 120 minutes.
Dried green-ball is placed in retort furnace and is warming up to 600 DEG C of calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 950 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
By the pelletizing block (ripe ball) after calcining at N
2under atmosphere and 1000 DEG C of constant temperature 5 minutes, recording high temperature hot strength was 3.99MPa (in Fig. 3 the 12nd sample).
Ripe ball is cooled to about 100 DEG C, then is dropped in furnace of calcium carbide, 1900 DEG C time, react 40 minutes, obtain calcium carbide, as Fig. 4 analysis.
Embodiment 6
White lime is pulverized, sieves, divide with sieve focusing dressing sieve, make the granularity of two raw materials be 0.2mm.
The NaHSO of 1.5% is added in the white lime of above-mentioned granularity
4, fully stir, then prepare burden with the mass ratio of coke powder according to 3:1, then add and account for the coal tar of mixture weight ratio 20% and the water of 10% respectively, stir.
The material of mixing is placed on coldmoulding in embedding model machine (forming pressure is 45MPa), obtains the cylinder green-ball of 30g.Being placed on by this green-ball is connected with in the loft drier of oxygen, is heated to 150 DEG C with 20 DEG C/min temperature rise rate, freeze-day with constant temperature 120 minutes.
Dried green-ball is placed in retort furnace and is warming up to 650 DEG C of calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 1000 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
By the pelletizing block (ripe ball) after calcining at N
2under atmosphere and 1000 DEG C of constant temperature 5 minutes, recording high temperature hot strength was 7.86MPa (in Fig. 3 the 11st sample).
Ripe ball is cooled to about 100 DEG C, then is dropped in furnace of calcium carbide, 1800 DEG C time, react 40 minutes, obtain calcium carbide (as Fig. 4 analysis).
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claim of the present invention and appurtenance completely, implementation procedure and the same the various embodiments described above of method; And non-elaborated part of the present invention belongs to techniques well known.
The above; be only part embodiment of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art are in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (9)
1. a carbide slag and coke powder coforming prepare the method for calcium carbide, it is characterized in that: modification is carried out to the calcium carbide ground-slag of purifying, and by modified calcium carbide ground-slag, coke powder and organic binder bond and the abundant mix and blend of water, the balling-up agglomerate that then pressurizes prepares carbon containing carbide slag-green-ball; First green-ball controls through oxidation drying, then carries out calcining control acquisition CaO carbonaceous pelletizing-ripe ball, and calcining after-ripening ball is substituted conventional block material, for the production of calcium carbide.
2. method according to claim 1, is characterized in that: the properties-correcting agent for calcium carbide ground-slag adopts acid or acid salt; Described acid is selected from by one or both in hydrochloric acid, nitric acid, phosphoric acid, acetic acid, sulfuric acid, and described acid salt is selected from by NaHSO
4, NaH
2pO
4, NaHSO
3, Ca (H
2pO
4)
2, Na
2hPO
4, CaHPO
4, Ca
3(PO
4)
2in one or both.
3. method according to claim 2, is characterized in that, the consumption of described acid or acid salt is 0.5 ~ 3% of calcium carbide ground-slag total mass.
4. method according to claim 1, is characterized in that, described carbide slag powder and coke powder need grind and sieve, and its granularity is less than 3mm, is preferably less than 1mm.
5. method according to claim 1, it is characterized in that: described organic binder bond is two or more combination formed in starch, Mierocrystalline cellulose, coal tar, mink cell focus, cracked oil, coking coal, pitch class, rubber-like, resol class and organic acid, and in binding agent, the mass ratio of each component is 1:1.
6. method according to claim 1 or 5, it is characterized in that: the mass ratio of described modified carbide slag powder, coke powder, organic binder bond and water: modified carbide slag: coke powder: organic binder bond: water=10:(2.5-5): (1-3): (0.5-2.5), the addition of organic binder bond is the 5%-30% of calcium carbide ground-slag and coke powder gross weight, is optimized for 10%-15%; The addition of water is the 3%-20% of calcium carbide ground-slag and coke powder gross weight, is preferably 5%-15%.
7. method according to claim 1, is characterized in that: described pressurization balling-up agglomerate prepares the moulding pressure 20 ~ 50MPa in carbon containing carbide slag, is preferably 35 ~ 50MPa.
8. method according to claim 1, is characterized in that: described drying control is: under oxygen atmosphere, is heated to 80 ~ 180 DEG C with 20 DEG C/min temperature rise rate, and freeze-day with constant temperature 120 minutes, temperature is preferably 100-150 DEG C.
9. method according to claim 1, is characterized in that: described calcining control is: by dried green-ball 500-700 DEG C of scope calcining at constant temperature 30 minutes, then calcining at constant temperature 30 minutes at being warming up to 800 ~ 1000 DEG C, and calcination atmosphere is N
2or CO
2or Ar.
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