CN104556228B - Carbon ferrochrome liquid phase legal system chromate processes - Google Patents

Carbon ferrochrome liquid phase legal system chromate processes Download PDF

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CN104556228B
CN104556228B CN201310485643.5A CN201310485643A CN104556228B CN 104556228 B CN104556228 B CN 104556228B CN 201310485643 A CN201310485643 A CN 201310485643A CN 104556228 B CN104556228 B CN 104556228B
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ferrochrome
product
carbon
solution
trivalent
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CN104556228A (en
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唐翔
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C01G37/14—Chromates; Bichromates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/037—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/06—Oxalic acid
    • C07C55/07—Salts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The present invention relates to a kind of carbon ferrochrome liquid phase legal system chromate processes, with carbon ferrochrome as raw material, high-temperature high-voltage reaction container or High Temperature High Pressure are not required to () in normal-pressure reaction kettle, add extraordinary reacting substance, crome metal in ferrochrome is converted into into Cr VI, high purity chromic acid product salt, iron in ferrochrome take high-purity iron oxides, silicon and carbon high purity metallic silicon and high-purity carbon in ferrochrome, other reacting substances are converted into high-purity chemical products.Whole technological process, production are efficient, energy-conserving and environment-protective, without waste residue, without waste gas, non-wastewater discharge.Meet the requirement of Modern Green economic development.With good Business Economic Benefit, environmental benefit and social benefit.

Description

Carbon ferrochrome liquid phase legal system chromate processes
Technical field
The present invention relates to a kind of carbon ferrochrome liquid phase legal system chromate processes, belong to metallurgic product as raw material production chromic salts The technical field of chemical products, change it is original produce chromate processes by raw material roasting method of chromite, be particularly suitable for existing Some chromate enterprise enlargings, the production of reconstruction chromate and newly-built chromate enterprise.
Background technology
Chromate is the important source material and intermediate of industrial products production, and the product of national economy 10 can use chromium Hydrochlorate product, as scientific and technological expanding economy, the application of chromic salts product are quite varied, is applied to chemical industry, metallurgy, plating, metal The fields such as process, timber, ceramics, weaving, printing and dyeing, pigment, dyestuff, papermaking, national defence.
The applicating history of chromic salts product is long, and China is the founder of chromium salt production and application, early in period in Spring and Autumn and Warring States, Qin Hanshi Phase has invented the production of chromic salts and has obtained good application, one layer 10 microns of the chromium from unearthed bronze double-edged sword plated surface Oxide understands that much earlier than western countries, Chinese have intelligent capability research invention than external to the chromium salt production technology of China More advanced chromium salt production technology, changes existing chromium salt production general layout.
Original chromate production method mainly using having calcium roasting and calcium-free roasting technique, with chromite as raw material in addition The raw materials such as auxiliary soda, dolomite, Calcium Carbonate, Jing after 1200 DEG C of high-temperature roastings, through water logging, roguing, filtration, evaporation knot It is brilliant, dry, chromic acid product salt is obtained.The method input is big, and power consumption is high, and raw material availability is low, high cost, produces a large amount of in production Waste residue, waste gas, the detoxication such as waste water it is difficult, huge harm is produced to environment and the mankind.
" by the method for chromite Jing producing sodium chromate by calcium-free calcination " of Gansu Jin Shi Chemical Co., Ltd.s invention, application Number：200710017747.8；Notification number：CN101045559；Publication date：2007.10.03, although the technique employ and roast without calcium Burn, but it is low to there is raw material availability, power consumption is high, pollution is big, the problem that the chromium residue of generation is processed.
Tianjin Paisen Technology Co., Ltd. invention " carbon ferrochrome hydrothermal oxidization prepares the alkali metal salt of dichromic acid Method ", number of patent application：PCT/CN2010/078336, notification number：WO0212058801A1, the day for announcing：May 23 in 2012 Day, the technique adds high purity oxygen gas and aqueous slkali, the oxidation of Jing high-temperature liquid-phases to produce chromic salts by raw material of ferrochrome.Technique exists following Problem；1. high pure oxygen consumption is big, and expensive, the cost of material such as ferrochrome, alkali is too high, has a strong impact on enterprise profit.2. technique is needed Oxygen to be continuously added, oxygen and reactant are easily interrupted, and affect response speed.The equipment such as 3 autoclaves, large-scale oxygen container are thrown Money is big, there is potential safety hazard.4. the slag of siderochrome containing Cr VI for producing in technique washes with water and is very difficult to, except clean, easily produce secondary Pollution, it is impossible to comprehensively utilize.
Therefore, chromate production technology is had as production cost is high, raw material does not make full use of, and profit is low, in production The waste residue containing Cr VI for producing scientifically is not processed and is utilized, easily to environmental danger.Now in the urgent need to a kind of raw Produce efficiency high, the good method of new technique of energy-conserving and environment-protective.
The content of the invention
It is an object of the invention to clean energy-saving production high-quality chromate and side-product, environmental protection and resource, promote Economy and social development.
The purpose of the present invention is reached by following measure：
A kind of carbon ferrochrome liquid phase legal system chromate processes, it is characterised in that：Ferrochrome is worn into into fine powder, acid adding dissolving chromium Ferrum, adds oxidation reaction material, heating oxidation, by trivalent chromium oxidation into Cr VI, make chromic acid product salt and Ferrox., Silicon, carbon and hydrogen product, step are as follows：
(1). ferrochrome is worn into into 100 mesh above fine powders, is put in reactor, added enough acid, be sufficiently stirred for, reacted molten Solution, makes ferrochrome generate trivalent chromic ion and ferrous ion, and collects hydrogen to obtain hydrogen product, add water to be changed into soluble substance Ion, obtains containing trivalent chromic ion and ferrous ions soln, and in solution, precipitate is silicon, and float is carbon, by solution mistake respectively Filter, obtains filtrate and filtering residue, and filtrate is trivalent chromic ion and ferrous ions soln；
(2). filtering residue is scrubbed, separates, and is dried, and product silicon and carbon is obtained；
(3). oxalic acid will be added in step (1) filtrate trivalent chromic ion and ferrous ions soln, be precipitated as ferrous ion Ferrox., filters, and filtrate is trivalent chromic ion solution, and filter cake is Ferrox., washs, crystallizes, is dried, product oxalic acid is obtained It is ferrous；
(4). Sodium Dimethyldithiocarbamate or sulfide will be added in step (3) filtrate trivalent chromium solutions, remove other micro metals from Son, filters to obtain trivalent chromic ion solution；
(5). will add in obtained part trivalent chromium solutions in step (4) carbonate or bicarbonate or hydroxide or Ammonia, makes trivalent chromium be precipitated as chromic oxide gel completely, filters, washs, crystallizes, is dried, product chromic oxide gel, chromic oxide gel is obtained It is middle to add oxidation reflection material：Percarbonate or persulfate or hydrogen peroxide or oxygen or peroxide salt or permanganate or secondary chlorine Hydrochlorate and carbonate and alkali, agitating heating, oxidation reaction, in making solution, trivalent chromium oxidation is Cr VI, and chromatedsolution is obtained Or dichromate solution；
(6). oxidation reaction material will be added in obtained another part trivalent chromium solutions in step (4)：Percarbonate or Persulfate or hydrogen peroxide or oxygen or peroxide salt or permanganate or hypochlorite and carbonate and alkali, agitating heating, oxygen Change reaction, trivalent chromium oxidation is Cr VI in making solution, and chromatedsolution or dichromate solution is obtained；
(7). by chromatedsolution or dichromate solution, evaporative crystallization, separate, be dried, product chromate or weight is obtained Chromate；
(8). acid acidifying will be added in chromatedsolution, using sulfuric acid process or carbonizatin method or electrolysis, make chromatedsolution Dichromate solution is generated completely, and evaporative crystallization, separation, drying are obtained product bichromate.
It is in order to preferably make the inventive technique be applied in the industrialized production of chromate as soon as possible, first in 2013 years The moon is tested on the 28th.
Specific embodiment
1. 20kg ferrochrome (chromium is taken：49%, ferrum：36.%, carbon：8%, 7%), levigate 100 mesh is put into 100L reactors to silicon In, 40kg sulphuric acid is added, is stirred 1.5 hours, and is collected hydrogen, after observing response is complete, hydrogen 0.8kg is obtained, add water to stir Mix 10 minutes, filter, obtain filtrate and filtering residue, filtering residue is scrubbed, separate, be dried, resultant metal Si is obtained：1.4kg and C： 1.6kg。
2. oxalic acid 15kg is added in filtrate, Fe is made2+FeC is precipitated as completely2O4, filter, wash, crystallize, be dried, be obtained and produce Product FeC2O418kg。
3. add sodium peroxide 20kg, sodium peroxydisulfate 10kg, sodium carbonate 20kg, stirring to heat up in filtrate, make Cr in solution3+ It is oxidized to Cr6+, chromatedsolution (CrO is obtained4 2-)。
4. chromatedsolution (CrO4 2-) middle addition sulphuric acid acidifying, evaporative crystallization is separated, dry, prepared product sodium dichromate 24kg。
Facts have proved that the invented technology is advanced, without the need for high-temperature high-pressure reaction kettle, room temperature can high purity chromic acid product salt, Produce chromate speed fast, ferrochrome and utilization rate of raw materials 100%, in ferrochrome, all substances composition and reacting substance are totally converted For the chemical products of high-quality high value.In production process without waste gas, without waste water, without waste sludge discharge.With good practicality, Feasibility, has good economic benefit, environmental benefit and social benefit.

Claims (1)

1. a kind of carbon ferrochrome liquid phase legal system chromate processes, it is characterised in that：Ferrochrome is worn into into fine powder, acid adding dissolves ferrochrome, Oxidation reaction material, heating oxidation is added by trivalent chromium oxidation into Cr VI, to make chromic acid product salt and Ferrox., silicon, carbon And hydrogen product, step is as follows：
(1). ferrochrome is worn into into 100 mesh above fine powders, is put in reactor, added enough acid, be sufficiently stirred for, reaction dissolving, Make ferrochrome generate trivalent chromic ion and ferrous ion, and collect hydrogen to obtain hydrogen product, add water make soluble substance be changed into from Son, obtains containing trivalent chromic ion and ferrous ions soln, and in solution, precipitate is silicon, and float is carbon, and solution is filtered respectively, Filtrate and filtering residue are obtained, filtrate is trivalent chromic ion and ferrous ions soln；
(2). filtering residue is scrubbed, separates, and is dried, and product silicon and carbon is obtained；
(3). oxalic acid will be added in step (1) filtrate trivalent chromic ion and ferrous ions soln, make ferrous ion be precipitated as oxalic acid Ferrous iron, filters, and filtrate is trivalent chromic ion solution, and filter cake is Ferrox., washs, crystallizes, is dried, product oxalic acid is obtained sub- Ferrum；
(4). Sodium Dimethyldithiocarbamate or sulfide will be added in step (3) filtrate trivalent chromium solutions, remove other micro metal ions, mistake Filter to obtain trivalent chromic ion solution；
(5). carbonate or bicarbonate or hydroxide or ammonia will be added in the trivalent chromium solutions of obtained part in step (4) Water, makes trivalent chromium be precipitated as chromic oxide gel completely, filters, washs, crystallizes, is dried, product chromic oxide gel is obtained, in chromic oxide gel Add oxidation reaction material：Percarbonate or persulfate or hydrogen peroxide or oxygen or peroxide salt or permanganate or hypochlorous acid Salt or carbonate or alkali, agitating heating, oxidation reaction, make trivalent chromium oxidation in solution be Cr VI, be obtained chromatedsolution or Dichromate solution；
(6). oxidation reaction material will be added in obtained another part trivalent chromium solutions in step (4)：Percarbonate or over cure Hydrochlorate or hydrogen peroxide or oxygen or peroxide salt or permanganate or hypochlorite or carbonate or alkali, agitating heating, oxidation are anti- Should, in making solution, trivalent chromium oxidation is Cr VI, and chromatedsolution or dichromate solution is obtained；
(7). by chromatedsolution or dichromate solution, evaporative crystallization, separate, be dried, product chromate or dichromic acid is obtained Salt；
(8). acid acidifying will be added in chromatedsolution, using sulfuric acid process or carbonizatin method or electrolysis, make chromatedsolution complete Dichromate solution is generated, evaporative crystallization, separation, drying are obtained product bichromate.
CN201310485643.5A 2013-10-10 2013-10-10 Carbon ferrochrome liquid phase legal system chromate processes Active CN104556228B (en)

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CN105016387B (en) * 2015-07-20 2017-09-15 中国科学院过程工程研究所 A kind of processing method of chromic salts mud
CN107236967A (en) * 2016-03-28 2017-10-10 唐翔 The preparation method of high-purity refractory metal and device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1526646A (en) * 2003-09-23 2004-09-08 史培阳 Prepn of chromium subsulfate
CN102583540A (en) * 2012-03-15 2012-07-18 甘肃锦世化工有限责任公司 Method for preparing chrome oxide black and co-producing ferrous oxalate by utilizing chrome-containing cast iron acid dissolution

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1526646A (en) * 2003-09-23 2004-09-08 史培阳 Prepn of chromium subsulfate
CN102583540A (en) * 2012-03-15 2012-07-18 甘肃锦世化工有限责任公司 Method for preparing chrome oxide black and co-producing ferrous oxalate by utilizing chrome-containing cast iron acid dissolution

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