CN104876818A - Method for reducing inorganic compound by water as hydrogen source or by molten alkali and use thereof - Google Patents
Method for reducing inorganic compound by water as hydrogen source or by molten alkali and use thereof Download PDFInfo
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Abstract
The invention relates to a method for reducing an inorganic compound by water as a hydrogen source to synthesize an organic compound or hydride and a use thereof. The related hydrogen acceptors comprise inorganic or organic compounds such as carbon dioxide, carbonate, acetic acid and urea containing C=O groups, and also comprise inorganic compounds such as nitrogen dioxide, sulfur dioxide, sulfate and nitrate. The method utilizing water as a hydrogen source can realize high efficiency and low cost conversion of the inorganic compounds containing C=O groups into alcohol organics or conversion of inorganic compounds containing S=O and N=O groups into corresponding hydrides. The invention also relates to a method for reducing carbon dioxide, sulfur dioxide or nitrogen dioxide into carbon simple substance, sulfur simple substance or nitrogen by molten alkali catalysis and a use thereof and also relates to a method for reducing a metal hydroxide into a corresponding metal simple substance by molten alkali catalysis and a use thereof.
Description
One, technical field
The present invention relates to a kind of take water as hydrogen source reduction mineral compound synthesis of organic substance or the method for hydride and purposes, namely adopts with water the hydrogen transfer reactions of the carbonyl reduction type being hydrogen donor.So-called hydrogen transfer reactions is in the presence of a catalyst, as hydrogen source, hydrogen acceptor is carried out to the reduction reaction pattern reduction mineral compound of hydrogenation or hydrogenolysis with hydrogen donor.The hydrogen acceptor that the present invention relates to is the inorganic or organic compound containing C=O base such as carbonic acid gas, carbonate, acetic acid, urea, and, because the present invention also regards carbonyl compound as a kind of broad sense as the inorganics containing S=O base and N=O base, so the hydrogen acceptor that the present invention relates to also comprises the mineral compound such as nitrogen peroxide, sulfurous gas, vitriol, nitrate.Adopt method of the present invention, utilize water as the purposes of hydrogen source, can high-level efficiency, low cost the above-mentioned inorganics containing C=O base is converted into alcohol type organic, or the inorganics containing S=O and N=O base is converted into corresponding hydride, such as, nitrogen peroxide is converted into ammonia.In addition, the invention still further relates to and adopt molten caustic soda catalysis that carbonic acid gas or sulfurous gas or nitrogen peroxide are reduced to method and the purposes of carbon simple substance or sulphur simple substance or nitrogen; Relate to the method and the purposes that adopt molten caustic soda catalysis metal hydroxides to be reduced to corresponding metal simple-substance.Method of the present invention and purposes, the Controlling and developing new forms of energy of combustion product gases are organically combined, provide one while zero carbon emission reduction, prepare various organic practicable technological line, and provide technical strategies for Metal smelting field.
Two, background technology
Natively little as the bibliographical information of the organic reaction of hydrogen source reducing carbonyl about water, reduce CO about water as hydrogen source
2for organism, except the photosynthesis that people know, it is the approach of the chemosynthesis reaction by unglazed photograph if say, then have never heard of especially, because this wherein contains the newfound principles of chemistry, and there is the problem (auspiciously to see " reaction coupling phenomenon and modern thermodynamics categorizing system " literary composition) not meeting classical thermodynamics law.Such as, under the envrionment temperature of the Nature and the condition of pressure, what carbonic acid gas and concentrated sodium hydroxide reactant aqueous solution generate or more clearly ask a question: what the solids of separating out after one glass of concentrated sodium hydroxide aqueous solution being exposed absorbing carbon dioxide was in atmosphere what answer up to now on all Middle School Chemistry Textbook 's all assert generation is sodium carbonate, organism can not be generated, but, the applicant proves by experiment, mainly a kind of two carbon organic combounds of generation and not sodium carbonate; And at identical conditions, it is a kind ofly connect disulfide and be not S-WAT that sulfurous gas and concentrated sodium hydroxide react what mainly generates, so, experiment can prove, Middle School Chemistry Textbook ' is defective about the discussion of this respect, this discovery, use water as the basis on the basis into hydrogen source reducing carbon dioxide synthol type organic just, also be the basis used water as the hydrogen source reduction method of mineral compound and the basis of purposes, discuss the visible following unexposed paper delivered temporarily in detail.
Water is as the reaction of hydrogen source reducing carbonyl or hydroxyl
1, introduction
Carbonyl or hydroxyl belong to vitochemical concept and term, and at organic chemistry category, water has frequency alcohol linked reaction in Cannizzaro reaction, the aqueous solution etc. as the reduction reaction of hydrogen source, but theme is herein CO
2, SO
2, NO
2, CO, Na
2cO
3, the mineral compound such as urea is all as the carbonyl compound in organic chemistry concept, and introduce the principle of vitochemical carbonyl or hydroxyl reduction reaction, with organism such as water Reactive Synthesis oxyacetic acid, ethylene glycol, ethanol, quadrol, glycine, acetylene, and, just easy by CO by the catalyzed reaction of a step molten caustic soda
2, SO
2, NO
2be converted into carbon simple substance, sulphur simple substance, nitrogen, thus by zero carbon emission reduction and tap a new source of energy the two organically combine, in other words, while improvement combustion product gases reaches zero carbon emission, multiple combustible organic or hydride can be developed, create a large amount of fuel, develop a kind of heat energy new forms of energy of bad flue gas zero release.
Reaction as herein described, yet there are no the report of any document and the even any information of data, is further research and summary on the basis of newfound following experimental example (example 1),
NaOH or the KOH aqueous solution of example 1, throwing 600 gram 35% ~ 50% is in reactor, and start and stir, control temperature-10 ~ 40 DEG C, slowly adds CO
2gas totally 10 ~ 40 grams, stirring reaction 5 ~ 15 minutes, cooling, crystallization, filtration, the solids leached is a kind of two carbon organic combounds, CO
2transformation efficiency is 99%, and the yield of two carbon organic combounds is more than 80%, and whole process is thermopositive reaction, and this two carbon organic combounds can make neutrality or alkalinity potassium permanganate variable color.
From example 1, do not add any catalyzer, only adopt sodium hydroxide or potassium hydroxide aqueous solution and CO
2two kinds of raw materials, this close under the condition of large natural environment at normal temperature, normal pressure, just synthesize organism expeditiously.This organism can react oxalic hydrogen sodium etc. with neutral potassium permanganate, and be also reduced to ethylene glycol and ethanol by catalyzed reaction, above-mentioned example 1 has been overthrown on junior middle school chemistry textbook and absorbed CO about by strong caustic
2generate sodium carbonate and organic conclusion can not be generated, becoming the basis on the basis of reaction described herein.
About the problem of recycle carbonic acid gas synthol, analyze feasible in theory even if most of expert thinks, but will accomplish technically and economically also practical, then the possibility at least in 20 years is from now on little, if under the processing condition of example 1, only use the NaOH aqueous solution and CO
2reactive Synthesis organism is then considered to impossible especially, because all middle school's textbooks are all said what synthesize thus is inorganic carbonate, but, surprisingly, unexpectedly from no one, analysis and verifying had in earnest been carried out to the carbonate that above-mentioned what is called is synthesized since a century, notice that this carbonate can make Neutral Potassium Permanganate Liquid change green potassium manganate solution into from no one, and inorganic carbonate there is no this function, thus thus query being proposed, the author recognizes to there is this query suddenly in recent years.And, the exothermic effect of example 1 does not meet the classical law of thermodynamics (civilian see " reaction coupling phenomenon and modern thermodynamics categorizing system ") yet, main reason is carbonic acid gas is inorganics, be just likely converted into organism, but carbonic acid gas belongs to the final product of burning after must adding protium, highly stable, approximate rare gas element, therefore the reaction of hydrogenation of carbon dioxide synthesis of organic substance is difficult to carry out, and needs to input a large amount of energy, and transformation efficiency is very low, preparation cost is very high.But from the angle analysis of organic reaction, this final conclusion for carbon dioxide reduction reaction is but apparent error.Molecular weight of carbon dioxide is little, and the spatial obstacle affecting reactive behavior is little, and the two carbonyls particularly containing accumulation in carbon dioxide molecule structure, obviously belong to a kind of carbonyl compound of lively type, especially in carbon dioxide molecule structure except exclusive this pair of carbonyl, not containing other any elements such as hydrogen, the aldol condensation that general carbonyl compound often has can not be there is, the emulative side reaction of the types such as Cannizzaro, therefore derive according to the rule of carbonyl reduction reaction: for Carbonyl addition or carbonyl reduction coupling these two kinds reactions, carbonic acid gas should belong to one of compound that in carbonyl one compounds, (in addition to carbon monoxide) reactive behavior is the strongest and selectivity is the highest, therefore carbonic acid gas should belong to one of the most excellent raw material of synthesis two carbon organic combounds.The discovery of example 1, demonstrates above-mentioned about CO just
2the derivation of reduction reaction, just CO in its principle
2as a kind of carbonyl compound, the principle of frequency alcohol linked reaction classical in organic chemistry and hydrogen transfer reactions is adopted to carry out the reaction of example 1, so, further developed CO, SO again on this basis
2, NO
2, Na
2cO
3, the carbonyl compound such as urea reduction reaction, in order to reduce costs, mainly have selected and using water as hydrogen source, also can select alcohol, methane, NH in theory
3etc. all hydrogeneous proton compounds as hydrogen source.
About the principle of water herein as hydrogen source reduction hydroxyl, as described below:
2, the reduction reaction of meta oxyhydroxide
Oxyhydroxide can appellation oxy-compound at organic chemistry category, and herein all compounds containing-OH base, is referred to as oxyhydroxide, comprises metal hydroxides, such as Zn (OH) no matter inorganic or organic
2, Al (OH)
3, Fe (OH)
2, Cu (OH)
2deng, also comprise the organic compound containing hydroxyl such as alcohol, phenol, carboxylic acid, even comprise the compound elements such as sulphur, nitrogen, phosphorus, boron, silicon being connected with hydroxyl (-OH base), such as sulfuric acid, nitric acid, phosphoric acid, boric acid, silicic acid etc.Following a few class is divided into: a) with carbon glycol or with carbon polyol about metastable hydroxyl groups compound defined herein (or meta oxyhydroxide), b) enol, alkynol, pyrogallol one compounds, c)
(hemiacetal),
one compounds, d) hydroxylamine compound, e) heat decomposition temperature is metal or the Non-metal hydroxides of less than 200 DEG C, has zinc hydroxide, aluminium hydroxide, ironic hydroxide, copper hydroxide etc., also has positive silicic acid, boron hydroxide etc., the author finds that the hydroxyl in these meta oxyhydroxide is easily eliminated by strong alkali aqueous solution or highly basic alcoholic solution and forms hydroxyl radical free radical, simultaneously occur automatic oxidation reaction and with water or alcohol generation hydrogen transfer reactions, above-mentioned so-called " meta " one word be exactly the term in the meaning of this reaction, construct thus using above-mentioned meta oxyhydroxide as hydrogen acceptor or the intermediate as carbonyl hydrogen acceptor, with water, the protic solvents such as alcohol are the new model of the hydrogen transfer reactions of hydrogen donor, especially only need to use water as hydrogen donor, just can expeditiously by carbonic acid gas, carbon monoxide, carbonate, borate, sulfurous gas, the inorganicss such as nitrogen peroxide are converted into organism or flammable hydride by hydrogen transfer reactions, for carbon emission reduction, new forms of energy, desulfurization, denitration, new basis has been established in the technical progress in the fields such as the hydrogenation of carboxylic acid.
The definition of 2.1 reactions
Containing the same carbon diol intermediates that the compound of-OH base or carbonyl and water addition reaction generate, as long as there is the process that de--OH base generates HO free radical in strong alkali solution, then this kind of compound or intermediate, no matter be inorganics or organism, be referred to as meaning meta oxyhydroxide, using this meta oxyhydroxide for raw material or intermediate are called the reduction reaction of meta oxyhydroxide as the suction hydrogen reduction reaction that hydrogen acceptor is participated in.
Such as, in formalin, the formaldehyde of 99.99% exists with the form of same carbon glycol or dihydroxyl methane, there is the reaction that de--OH base generates HO free radical in the easy and NaOH aqueous solution, formaldehyde autoxidation is formic acid, the reaction of drawing hydrogen in water occurs, methanol while dehydroxylation, the mechanism of this Cannizzaro reaction classical just, if add zinc powder, can suppress the automatic oxidation reaction of formaldehyde, primary product is vicinal diamines and methyl alcohol., in sodium hydroxide or potassium hydroxide aqueous solution, all easily there is the reaction of this automatic oxidation reduction, add the HO scavenger of free radicals such as zinc powder, this automatic oxidation reaction can be suppressed and select autoreduction to react in the enol such as aldehydes and the pyrogallol classes such as phenyl aldehyde.
The principle of 2.2 reactions
From the above, the principle of reaction derives from the research and summary of reacting the automatic oxidation reduction of classics.In addition, a hard fact is there is in organic chemistry, the general organism containing aldehyde radical can not steady in a long-termly exist in the alkaline aqueous solution, the more typically Cannizzaro reaction of phenyl aldehyde and frequency alcohol linked reaction in aqueous, what is interesting is under almost identical processing condition, do not add zinc powder and mainly Cannizzaro reaction occurs, main generation alcohol linked reaction frequently after adding zinc powder, these two kinds reaction each other competition and all using water as hydrogen source, water has participated in reaction as a kind of hydrogen donor in other words.If CO
2regard as that carbonyl compound of similar phenyl aldehyde, due to CO
2not containing protium in molecular structure, Cannizzaro reaction can not occur, but still alcohol linked reaction frequently can occur generate two carbon organic combounds, we know already, generally all belong to organism containing oxygen c2 compounds, this just above-mentioned example 1 use CO
2with the principles of chemistry of water synthesis of organic substance easily, experiment can prove, below 20 DEG C, and CO
2generation sodium carbonate more difficult with 35%NaOH reactant aqueous solution, what mainly generate is a kind of two carbene alkoxide.The good authentication of example 1, has absolutely proved employing CO
2be raw material with water, under the condition of large natural environment, synthesis of organic substance is a very simple thing in fact, and a mysterious or thing simultaneously can releasing heat energy, above-mentioned example 1 is not only water and is converted into organism or hydride is laid a good foundation, for the research of origin of life provides new thinking as hydrogen source reduction inorganic carbonyl compound yet.
On the basis of example 1, the author completes carbonate or CO further
2with the alcohol mixture (example 2, example 4) of water Reactive Synthesis oxyacetic acid and ethylene glycol+ethanol+methyl alcohol; Carbon monoxide and water Reactive Synthesis acetylene (example 3); Urea and water Reactive Synthesis quadrol (example 5); Acetic acid and water Reactive Synthesis ethanol and butyleneglycol (example 6); NO
2with water Reactive Synthesis ammonia and hydrazine hydrate (example 7, example 8) etc. series of experiments example, these experimental examples all yet there are no the report of any document and data, they all meet above-mentioned identical take water as the hydrogen transfer reactions principle of hydrogen donor, also contain two new principles as described below:
2.2.1 carbonyl (C=O) compound, comprise the compound containing P=O base, N=O base, S=O base, in dense strong alkali aqueous solution, especially, under adding at the same time the condition of active metal powder, be easily converted into the excited state of C-O key, P-O key, N-O key, S-O key, alkalescence is stronger, the trend forming excited state is larger, in other words, as long as oxygen supply double bond is equipped with the chemical environment of corresponding alkalescence, oxygen double bond (=O) must be converted into oxygen singly-bound (-O).Such as, the natural existence of phosphorous acid is the structural shape containing P=O double bond
its sodium phosphite formed in dense strong alkali aqueous solution is then the structural shape containing P-O singly-bound
belong to a kind of lively type of phosphorous acid.This excited state has stronger suction hydrogen function, and this cans be compared to the photoreduction hydrogen abstraction reaction of benzophenone one class, easily with the hydrogen donor generation hydrogen transfer reactions such as water, alcohol, hydrazine, formic acid, generation benzophenone from coupled product.The such as reaction of example 1 generates
excited state intermediate, draws H
2protium in O and sodium element define a kind of more stable enol sodium salt title complex, and the reaction of example 3 defines O-C ≡ C-O excited state intermediate, thus just likely use CO and H
2o Reactive Synthesis acetylene.In a word, the author finds that alkali has and optical, electrical identical function, the excited state that carbonyl compound can be made to be converted into lively type carries out reduction reaction, and at least dense highly basic has certain electron donation, has stronger reductibility (see following example 14) for carbonyl compound.The intensity of alkalescence can replace the energy of light or electricity to play a role in certain program, and why the reaction of this above-mentioned example 1 just becomes the principles of chemistry of exothermic effect.
2.2.2 sum up a large amount of organic reactions just can find, not only aldehyde compound unsuitable stable existence in strong alkaline aqueous solution, the unstable oxy-compound (such as with carbon glycol, enol, alkynol, azanol, hemiacetal etc.) known already also unsuitable stable existence in strong alkaline aqueous solution, easy generation automatic oxidation reduction reaction, produce HO free radical, this is found to be and uses water as hydrogen source reduction oxy-compound or the reaction of metastable state oxyhydroxide defined above of reducing are laid a good foundation.Such as dihydroxymethyl Sodium glycocollate strong alkali aqueous solution is reduced to N-methylsarcosine sodium (example 7), oxammonium hydrochloride is reduced to NH
3(example 8), though the bibliographical information of the industrialized developing there are no these examples, but also can be used as the illustration of above-mentioned meta oxyhydroxide reduction reaction mechanism, the automatic oxidation reduction reaction of classical Cannizzaro reaction, pyrogallol, gallic acid, aldehydes also can be illustratively, it should be noted that after adding zinc powder or the catalyzer such as Raney's nickel or iron powder, these reactions have oxygen to generate.The author thinks, the same principles of chemistry are followed in above-mentioned reaction, so-called unstable oxy-compound can be regarded as the metastable excited state of one, such as methylene glycol, even comprise hydrogen peroxide, in alkaline chemical environment, due to the impellent of transfer transport,-OH the base taken off is converted into HO free radical, the atom be connected to-OH is converted into corresponding free radical intermediate simultaneously, the function of the existing suction hydrogen of this intermediate is as hydrogen acceptor generation hydrogen transfer reactions, there is again the function generation dimerization reaction of autoimmunity syndrome, these all belong to the reaction of free radical type, so, as long as constantly the hydroxyl radical free radical of generation trapped in theory or be decomposed into O
2and H
2o, just can carry through to the end the reduction reaction of this class hydrogen acceptor, realize the transformation efficiency of more than 95%.
In this citing (example 4), concrete reaction mechanism is described, the alcohol mixture that the salt of wormwood that namely reduces using water as hydrogen source is oxyacetic acid and ethylene glycol+ethanol+methyl alcohol generates the reaction mechanism of the KOH of equivalent simultaneously:
K
2cO
3two kinds of excited state 1 and 2 (formula 1, formula 2) are activated in the 40%KOH aqueous solution,
Above-mentioned formula 1 is mechanism of nucleophilic addition to carbonyl group, formula 2 is carbonyl alcohol linked reaction mechanism frequently, 1 and 2 is the very unstable excited state of thermodynamics, the equilibrium constant of formula 1 and formula 2 is very little, 1 and 2 belong to typical metastable state oxyhydroxide, under the acting in conjunction of highly basic and zinc powder, easily take off-OH base new coupling reaction occurs and by-product KOH (formula 3, formula 4)
Formula 3 and formula 4 are reacted the HO free radical that generates or hydrogen peroxide and are captured in the environment of Zn and highly basic or decompose, molecular balance is progressively moved to right, the potassium formiate 3 generated and oxyacetic acid potassium 4 are under identical reaction conditions, the alcohol mixture (formula 5, formula 6, formula 7) of further reaction methanol+ethylene glycol+ethanol, 3+2H
2o → CH
3oH+O
2+ KOH (5) 4+2H
2o → HOCH
2cH
2oH+KOH+O
2(6)
From above-mentioned salt of wormwood and the organic mechanism of water Reactive Synthesis alcohols, under the katalysis of Zn/KOH reagent, the carbonate such as sodium carbonate, calcium carbonate, Quilonum Retard also can with water Reactive Synthesis alcohol type organic co-production sodium hydroxide or calcium hydroxide or lithium hydroxide, and, if using the character of S=O and N=O base as carbonyl, then sodium sulfate or nitric acid sodium and water reaction can synthesize Na
2s and hydrogen sulfide or NH
3co-production NaOH, this reaction pattern, for realizing inorganic mineral to be converted into organism or hydride co-production metal hydroxides is laid a good foundation.
In addition, the author finds that above-mentioned carbonyl or oxy-compound are in aprotic solvent, under the effect of melting highly basic, deoxidation can generate O free radical, such as, by CO
2or SO
2or NO
2pass in NaOH or KOH of anhydrous melting, mainly generate O
2with C simple substance or S simple substance or nitrogen, generate the sodium carbonate or S-WAT or Sodium Nitrite (example 14) that it has been generally acknowledged that hardly; Added by zinc hydroxide in NaOH and KOH of melting, main generation zinc simple substance, generates zinc oxide hardly, and wherein concrete reaction mechanism needs to be furtherd investigate further.
3, example and application thereof
Example 2, throw the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, start and stir, control temperature less than 40 DEG C, slowly adds 4 ~ 8 grams of CO
2in this reactor, heat up after 1 hour, control temperature less than 150 DEG C, simultaneously constantly or interval type ground remove gaseous product from reactor head spilling, reaction end is during content < 1% with the oxyacetic acid in liquid-phase chromatographic analysis reaction system, primary product is the alcohol mixture of ethylene glycol+ethanol+methyl alcohol, CO
2transformation efficiency is more than 99%, and alcohol mixture total recovery is more than 90%,
Example 3, throw the KOH aqueous solution of 100 gram 30 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, start and stir, control temperature less than 40 DEG C, slowly pass into 2 ~ 8 grams of CO gases, stirring reaction 10 ~ 18 hours, mainly generates acetylene, CO transformation efficiency is more than 95%, and acetylene yield is more than 90%.
Example 4, throws the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, drops into again the K of 10 ~ 40 grams
2cO
3solid, start and stir, control temperature 20 ~ 150 DEG C, in process constantly or remove the gas of generation with gap from reactor head, reaction end is during total content < 2% with the oxyacetic acid in liquid-phase chromatographic analysis reaction system and formic acid, primary product is alcohol mixture and KOH, the K of ethylene glycol+ethanol+methyl alcohol
2cO
3transformation efficiency be more than 95%, the yield of alcohol mixture and KOH is all more than 90%.
The recovery energy that example 4 is not only inorganic salt minerals is laid a good foundation, and has started the technological line that a kind of new non-electrical solution produces KOH.
Example 5, drop into the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, start and stir, slowly drop into again the urea solid of 10 ~ 40 grams, control temperature 20 ~ 150 DEG C, in process constantly or remove the NH of generation with gap from reactor head
3deng gas, primary product is the mixed amine of quadrol and methylamine, and conversion rate of urea is more than 95%, and the total recovery of mixed amine is more than 85%, and the thanomin yield of by-product is more than 10%.
Example 5 is applied to fertilizer industry not only can create larger economic benefit, because the price of quadrol product is more than 10 times of urea cost of material, and urea is CO
2one of major consumers product, therefore example 5 also has great importance for carbon emission reduction.
Example 6, throw the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, drop into again 10 ~ 40 grams of Glacial acetic acids, start and stir, control temperature 20 ~ 150 DEG C, in process constantly or remove the gas of generation with gap from reactor head, reaction end is during content < 1% with acetic acid in liquid-phase chromatographic analysis reaction system, primary product is ethanol and butyleneglycol, acetic acid transformation efficiency is more than 95%, and ethanol and butyleneglycol yield are more than 90%.
Example 6 shows can be hydrogen source reduction carboxylic acid one compounds with water.
Example 7, throw the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, start and stir, control temperature 40 ~ 150 DEG C, slowly passes into NO
210 ~ 20 grams, stirring reaction 4 ~ 18 hours, primary product is NH
3, NO
2transformation efficiency is more than 99%, NH
3yield is 80%, the N of by-product
2yield is more than 15%.
Example 8, throw the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, start and stir, control temperature less than 10 DEG C, slowly adds 10 ~ 20 grams of NO
2or nitrogen tetroxide, stirring reaction 4 ~ 18 hours, mainly generates hydrazine hydrate, NO
2transformation efficiency is more than 99%, and hydrazine hydrate yield is more than 80%.
Example 9, throw the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, start and stir, control temperature 10 ~ 150 DEG C, slowly adds 10 ~ 20 grams of volatile salts or bicarbonate of ammonia, or adds 20 grams of CO
2with 40 ~ 60 grams of strong aquas, stirring reaction 4 ~ 18 hours, mainly generates glycine, carbon ammonium or CO
2transformation efficiency be more than 99%, the yield of glycine is more than 85%.
Example 10, throws the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, starts and stir, control temperature 20 ~ 80 DEG C, slowly adds 10 ~ 20 grams of dihydroxymethyl glycine, insulation reaction 2 ~ 4 hours, generate N-methylsarcosine, yield is more than 87%.
Example 11, throw the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, start and stir, control temperature 20 ~ 90 DEG C, slowly adds 10 ~ 20 grams of oxammonium hydrochlorides, and stirring reaction 1 ~ 3 hour, mainly generates NH
3, yield is more than 90%.
Example 12, throw the KOH aqueous solution of 100 gram 40 ~ 48% and 10 ~ 20 grams of zinc powders or iron powder or Raney's nickel in reactor, drop into again 10 ~ 20 grams of water glass or Sodium Tetraborate, start and stir, control temperature 40 ~ 150 DEG C, stirring reaction 13 ~ 96 hours, constantly collects the gas overflowed from reactor head in process, primary product is silane or borine, and yield is more than 85%.
Example 13, the KOH throwing the NaOH and 49 gram 99% of 51 gram 99%, in reactor, drops into again 10 ~ 20 grams of Zn (OH)
2or Al (OH)
3or nickel hydroxide or stannic hydroxide or lead hydroxide or the metal hydroxides such as copper hydroxide or ironic hydroxide, start and stir, control temperature 200 ~ 700 DEG C, control pressure is high vacuum, stirring reaction 2 ~ 14 hours, the corresponding simple substance such as main generation zinc, aluminium, nickel, tin, lead, copper, iron, yield is more than 90%.
Example 14: throw 49 grams of anhydrous K OH and 51 gram anhydrous Na OH in reactor, start and stir, control temperature is 180 ~ 400 DEG C, slowly passes into CO
2or CO or SO
2or NO
2or each 50 grams of NO, in process, the gas timing generated by reaction is removed and recycle, with CO in gas chromatographic analysis reactor head gas from reactor head
2or SO
2or NO
2be reaction end during content < 1%, primary product is the simple substance of carbon simple substance or sulphur simple substance or nitrogen, and yield is 90%.
The flue gas of the coal combustion enterprise discharges such as thermal power plant is the arch-criminal causing topsoil, wherein primary pollution source CO just
2, SO
2, NO
2, but up to now also neither one meet the administering method of market economy rule, example 14 is that flue gas, the realization of target that simultaneously increases substantially economic benefit that enterprise fundamentally thoroughly administers Discharged form Coal Combustion is laid a good foundation.
Three, summary of the invention
An object of the present invention is to provide a kind of using water as hydrogen source reducing carbon dioxide, carbonate, bicarbonate of ammonia, urea, the compou nd synthesis oxyacetic acids such as acetic acid, ethylene glycol, ethanol, methyl alcohol, glycine, quadrol, the method of the organic compound such as butyleneglycol and purposes, in other words one of content of the present invention be exactly respectively with above-mentioned various compound containing carbonyl and water for raw material, use the principle of organic chemistry hydrogen transfer reactions, by the approach of chemosynthesis reaction, prepare various corresponding above-mentioned organic compound, reaching at least transformation efficiency is more than 90%, yield is the target of more than 80%.
1, water is as the alcohol mixture of hydrogen source reducing carbon dioxide or carbonate or formate or formaldehyde or bicarbonate of ammonia or urea or acetic synthesis oxyacetic acid or ethylene glycol+ethanol+methyl alcohol or glycine or quadrol or ethanol and butyleneglycol, the method of by-product NaOH (wherein Na represents sodium, potassium, calcium, lithium etc.), comprises several steps of following order.
Select conventional interval type or flow reactor, drop into the potassium hydroxide of 30 ~ 48% of calculated amount or sodium hydroxide or lithium hydroxide or calcium hydroxide aqueous solution or aqeous suspension, or all the alkaline aqueous solution such as the tetra-alkyl ammonium hydroxide aqueous solution dropping into 25% are in reactor, drop into again or the zinc of load calculated amount or iron or tin or plumbous or nickel or manganese or aluminium or all metal alloys such as metal simple-substance or Raney's nickel such as magnesium or copper in this reactor, control temperature-10 ~ 220 DEG C, drop into the carbonic acid gas of calculated amount or carbonate or formate or formaldehyde or bicarbonate of ammonia or the compound such as urea or acetic acid, retain certain reaction times, the principal product generated is the alcohol mixture of oxyacetic acid or ethylene glycol+ethanol+methyl alcohol or the alcohol mixture of glycine or quadrol or ethanol+butyleneglycol, if what drop into is carbonate or formate, then the potassium hydroxide of equivalent or sodium hydroxide or lithium hydroxide or calcium hydroxide is had to generate, if what drop into is urea, then ammonia is had to generate.
Then, solids in reaction system is filtered out, ethylene glycol in filtrated stock, ethanol, methyl alcohol, butyleneglycol are isolated qualified ethylene glycol or ethanol or methyl alcohol or butyleneglycol product by the method that conventional rectification is separated, and the metal solid thing reclaimed in this process can recycle.
2, water closes method and the purposes of hydrazine as hydrogen source reduction nitrogen peroxide or nitrogen tetroxide or nitrate or nitrite synthetic ammonia G&W, comprises several steps of following order:
Select conventional interval type or flow reactor, drop into the potassium hydroxide of 30 ~ 48% of calculated amount or sodium hydroxide or lithium hydroxide or calcium hydroxide aqueous solution or aqeous suspension, or all the alkaline aqueous solution such as the tetra-alkyl ammonium hydroxide aqueous solution dropping into 25% are in reactor, the zinc of input or load calculated amount again, iron, tin, plumbous, nickel, manganese, aluminium, magnesium, all metal alloys such as metal simple-substance or Raney's nickel such as copper are in this reactor, control temperature-10 ~ 150 DEG C, drop into the nitrogen peroxide of calculated amount or nitrogen tetroxide or nitrate or nitrite, retain certain reaction times, the principal product generated is ammonia and hydrazine hydrate, if what drop into is SODIUMNITRATE or Sodium Nitrite, the sodium hydroxide of by-product equivalent while of then, the ammonia water sorption enhanced generated is ammoniacal liquor,
Then, filtered out by the solids in reaction system, the hydrazine hydrate in filtrated stock is isolated qualified hydrazine hydrate product by the method for conventional rectification, the metal solid thing reclaimed in this process can recycle.
Two of object of the present invention be to provide a kind of with molten sodium hydroxide or molten potassium hydroxide or their mixture for catalyst reduction carbonic acid gas or nitrogen peroxide or sulfurous gas become method and the purposes of carbon simple substance and carbon monoxide or nitrogen and nitrogen protoxide or sulphur simple substance, namely be provided in the environment of melting highly basic, carbonic acid gas prepares the purposes of carbon simple substance and carbon monoxide as raw material single step reaction; Nitrogen peroxide prepares nitrogen and nitric oxide production purposes as raw material; Sulfurous gas prepares the purposes of sulphur simple substance as raw material, is mainly used in the field administering various combustion product gases, is applied to carbon emission reduction field.
By the method that carbonic acid gas or nitrogen peroxide or Sulphur Dioxide are carbon simple substance and carbon monoxide or nitrogen and nitrogen protoxide or sulphur simple substance, comprise several steps of following order:
Select conventional stirred reactor, drop into calculated amount without water sodium hydroxide or anhydrous potassium hydroxide or their mixture in this reactor, start and stir, control temperature 180 ~ 800 DEG C, add the carbonic acid gas of calculated amount or nitrogen peroxide or sulfurous gas, retain certain reaction times, periodically remove the oxygen overflowed from reactor head, the carbonic acid gas simultaneously overflowed or nitrogen peroxide or sulfurous gas is capable of circulation adds use, and collect the carbon monoxide or nitric oxide gas that overflow from reactor head simultaneously, then lower the temperature, conventional partition method is admittedly adopted to isolate carbon simple substance or sulphur simple substance, the sodium hydroxide reclaimed or potassium hydroxide can be recycled, if the nitrogen dropping into nitrogen peroxide generation can directly enter in atmospheric layer.
Three of object of the present invention be to provide a kind of with molten sodium hydroxide or molten potassium hydroxide or their mixture for catalyst reduction zinc hydroxide, ironic hydroxide, aluminium hydroxide, nickel hydroxide, all metal hydroxidess such as stannic hydroxide become method and the purposes of corresponding metal simple-substance, namely be provided in the environment of melting highly basic, zinc hydroxide or ironic hydroxide or aluminium hydroxide or all metal hydroxidess except alkali metal hydroxide such as hydrogen-oxygen nickel or stannic hydroxide prepare the purposes of zinc or iron or aluminium or all corresponding metal simple-substances such as nickel or tin as raw material single step reaction.
Zinc hydroxide or ironic hydroxide or aluminium hydroxide or all metal hydroxidess such as nickel hydroxide or stannic hydroxide are converted into the method for zinc simple substance or iron simple substance or aluminium simple substance or all corresponding metal simple-substances such as nickel simple substance or tin simple substance, comprise several steps of following order:
Select conventional stirred reactor, drop into calculated amount without water sodium hydroxide or anhydrous potassium hydroxide or their mixture in this reactor, start and stir, control temperature 180 ~ 800 DEG C, control pressure is high vacuum, slowly add the zinc hydroxide of calculated amount or ironic hydroxide or aluminium hydroxide or all metal hydroxidess except alkali metal hydroxide such as nickel hydroxide or stannic hydroxide, lower the temperature after insulation reaction certain hour, adopt the conventional solid method be separated, isolate zinc simple substance or iron simple substance or aluminium simple substance or all corresponding metal simple-substances such as nickel simple substance or tin simple substance, the sodium hydroxide reclaimed and potassium hydroxide can be recycled.
Four, embodiment
Embodiment 1
Drop into the potassium hydroxide of 100 gram 30 ~ 48% or sodium hydroxide or lithium hydroxide or calcium hydroxide aqueous solution or aqeous suspension; Or drop into the tetra-alkyl ammonium hydroxide aqueous solution of 100 gram 25% in reactor, drop into again 10 ~ 20 grams of zinc powders or Raney's nickel or reduced iron powder, start and stir, control temperature less than 40 DEG C, slowly adds CO
2or carbonate or formate or each 5 ~ 10 grams of formaldehyde, stirring reaction, after 1 ~ 2 hour, is progressively warming up to 90 DEG C, control temperature 90 ~ 220 DEG C, continues stirring reaction 14 ~ 24 hours, generates the alcohol mixture of oxyacetic acid and ethylene glycol+ethanol+methyl alcohol, CO
2or the transformation efficiency of carbonate or formate or formaldehyde is more than 95%, the total recovery of oxyacetic acid and alcohol mixture is more than 90%.
Then metal solid thing is filtered out under anaerobic, be kept in concentrated alkali solution, use in order to next batch, filtrated stock is isolated ethylene glycol, ethanol, methyl alcohol and hydroxy acid solution by conventional rectifying tower, if what drop into is sodium carbonate or sodium formiate, simultaneously by the method for conventional crystallization, filtration, the sodium hydroxide of by-product can be reclaimed.
Embodiment 2
Drop into the tetraethyl ammonium hydroxide aqueous solution of 100 gram 25% and 5 ~ 20 grams of magnesium powder or Raney's nickel in reactor, start and stir, control temperature-10 ~ 140 DEG C, slowly adds 5 ~ 10 grams of CO
2or salt of wormwood or potassium formiate, stirring reaction 4 ~ 48 hours, more slowly add and CO
2or salt of wormwood or the equimolar calcium hydroxide of potassium formiate, be down to room temperature, filter out solids, isolate MAGNESIUM METAL solids simultaneously, generate Calcium Glycolate solid, transformation efficiency is more than 95%, and the yield of Calcium Glycolate is more than 85%; Then use in sulfuric acid and Calcium Glycolate, after concentrated, obtain the hydroxy acid solution of 50%.
Embodiment 3
Drop into the potassium hydroxide of 100 gram 30 ~ 48% or sodium hydroxide or lithium hydroxide aqueous solution, or drop into the tetramethylammonium hydroxide aqueous solution of 100 gram 25%, add 10 ~ 20 grams of zinc powders or Raney's nickel simultaneously, start and stir, control temperature 10 ~ 80 DEG C, control pressure 1 ~ 4MPa, slowly adds 20 ~ 40 grams of bicarbonate of ammonia; Or slowly add 10 ~ 20 grams of CO
2with 20 ~ 40 grams of ammonias, insulation reaction 4 ~ 48 hours, generate glycine, transformation efficiency is 99%, and glycine yield is more than 80%.
Embodiment 4
Drop into the potassium hydroxide of 100 gram 30 ~ 48% or aqueous sodium hydroxide solution and 10 ~ 20 grams of zinc powders or reduced iron powder or Raney's nickel in reactor, start and stir, control temperature is 10 ~ 90 DEG C, control pressure is tiny structure, slowly adds 20 ~ 40 grams of urea, insulation reaction 4 ~ 48 hours, generate quadrol, by-product methylamine and ammonia, conversion rate of urea is more than 95%, and quadrol yield is more than 80%.
Embodiment 5
Drop into the potassium hydroxide of 100 gram 30 ~ 48% or aqueous sodium hydroxide solution and 10 ~ 20 grams of zinc powders or reduced iron powder or Raney's nickel in reactor, start and stir, control temperature 10 ~ 220 DEG C, slowly add 10 ~ 20 grams of acetic acid, insulation reaction 4 ~ 48 hours, generate ethanol and butyleneglycol, acetic acid transformation efficiency is more than 90%, and ethanol and butyleneglycol total recovery are more than 80%.
Embodiment 6
Drop into NaOH or KOH of 100 gram 99%, or the potassium hydroxide dropping into the sodium hydroxide of 51 gram 99% and 49 gram 99% is in reactor, start and stir, control temperature 180 ~ 400 DEG C, slowly adds 20 ~ 40 grams of CO
2or NO
2or SO
2, insulation reaction 4 ~ 48 hours, Formed simple substance and carbon monoxide or nitrogen and nitrogen protoxide or sulphur simple substance, CO
2or NO
2or SO
2transformation efficiency be more than 95%, the yield of Formed simple substance or sulphur simple substance and nitrogen is more than 80%, byproduct in process oxygen.
Embodiment 7
The KOH of NaOH or KOH dropping into 100 gram 99% or NaOH and 49 gram 99% dropping into 51 gram 99% is in reactor, start and stir, drain the air in reactor, control temperature 180 ~ 600 DEG C, slowly adds 10 ~ 30 grams of carbon monoxide or nitrogen protoxide, insulation reaction 1 ~ 48 hour, Formed simple substance or nitrogen, by-product oxygen simultaneously, CO or NO transformation efficiency is more than 95%, and the yield of carbon simple substance or nitrogen is more than 85%.
Embodiment 8
Throw the potassium hydroxide of 100 gram 30 ~ 48% or aqueous sodium hydroxide solution and 10 ~ 20 grams of zinc powders or reduced iron powder or Raney's nickel in reactor, start and stir, control temperature 40 ~ 180 DEG C, slowly add nitrogen peroxide or the sulfurous gas of 20 ~ 40 grams, insulation reaction 4 ~ 18 hours, generate ammonia or hydrogen sulfide, periodically collect ammonia or the hydrogen sulfide of generation or absorb ammonia or hydrogen sulfide, NO with water
2and SO
2transformation efficiency be more than 95%, ammonia yield is more than 90%, and the yield of hydrogen sulfide is more than 75%.
Embodiment 9
Throw KOH or the NaOH aqueous solution of 100 gram 30 ~ 48% and 10 ~ 20 grams of zinc powders or reduced iron powder or Raney's nickel or their mixture in reactor, start and stir, control temperature less than 10 DEG C, slowly adds the NO of 10 ~ 30 grams
2gas or nitrogen tetroxide liquid, insulation reaction 4 ~ 18 hours, generates hydrazine hydrate, NO
2or the transformation efficiency of nitrogen tetroxide is more than 95%, the yield of hydrazine hydrate is more than 80%.
Embodiment 10
Drop into sodium hydroxide or the potassium hydroxide of 100 gram 99%, or the potassium hydroxide dropping into the sodium hydroxide of 51 gram 99% and 49 gram 99% is in reactor, start and stir, control reactor pressure as far as possible close to perfect vacuum, control temperature 180 ~ 800 DEG C, slowly add zinc hydroxide or aluminium hydroxide or ironic hydroxide or all metal hydroxidess such as nickel hydroxide or stannic hydroxide, but do not add alkali metal hydroxide, insulation reaction 4 ~ 48 hours, cooling, leave standstill, adopt conventional solid-solid separation method, isolate zinc simple substance or aluminium simple substance or iron simple substance or all corresponding metal simple-substances such as nickel simple substance or tin simple substance, the transformation efficiency of the metal hydroxidess such as zinc hydroxide is more than 99%, the yield of the metal simple-substances such as zinc is more than 94%.
Embodiment 11
Throw the potassium hydroxide of 100 gram 30 ~ 48% or sodium hydroxide or lithium hydroxide or calcium hydroxide aqueous solution or aqeous suspension in reactor, start and stir, drop into again 10 ~ 20 grams of zinc powders or reduced iron powder or Raney's nickel or their mixture in this reactor, control temperature 40 ~ 140 DEG C, pressure is normal pressure, slowly add 20 ~ 40 grams of anhydrous sodium carbonates or salt of wormwood or sodium formiate or potassium formiate, insulation reaction 4 ~ 48 hours, generate oxyacetic acid and the ethylene glycol+alcohol mixture of ethanol+methyl alcohol and the sodium hydroxide of equivalent or potassium hydroxide, the transformation efficiency of sodium carbonate or salt of wormwood or sodium formiate or potassium formiate is 95%, the total recovery of the alcohol mixture of oxyacetic acid and ethylene glycol+ethanol+methyl alcohol is 90%, the yield of coproduct hydrogen sodium oxide or potassium hydroxide is 90%.
Claims (9)
1. water is as the purposes of hydrogen source reducing carbon dioxide or carbonate or formate or formaldehyde synthesis of hydroxy acetic acid, ethylene glycol, ethanol, methyl alcohol.
2. water is as hydrogen source reduction bicarbonate of ammonia or the purposes of carbonic acid gas or urea or acetic synthesis glycine or quadrol or ethanol and butyleneglycol.
3. water closes the purposes of hydrazine or hydrogen sulfide as hydrogen source reduction nitrogen peroxide or sulfurous gas synthetic ammonia G&W.
4., in the environment of melting highly basic, carbonic acid gas or nitrogen peroxide or sulfurous gas prepare the purposes of carbon simple substance and carbon monoxide or nitrogen and nitrogen protoxide or sulphur simple substance as raw material single step reaction.
5., in the environment of melting highly basic, zinc hydroxide or aluminium hydroxide or ironic hydroxide or all metal hydroxidess except alkali metal hydroxide such as nickel hydroxide or stannic hydroxide prepare the purposes of zinc simple substance or aluminium simple substance or iron simple substance or the corresponding metal simple-substance such as nickel simple substance or tin simple substance as raw material single step reaction.
6. water is as the alcohol mixture of hydrogen source reducing carbon dioxide or carbonate or formate or formaldehyde synthesis of hydroxy acetic acid and ethylene glycol+ethanol+methyl alcohol, and the method for by-product metal hydroxides, comprises several steps of following order:
Select conventional interval type or flow reactor, drop into the potassium hydroxide of 30 ~ 48% of calculated amount or sodium hydroxide or lithium hydroxide or calcium hydroxide aqueous solution or aqeous suspension, or all the alkaline aqueous solution such as the tetra-alkyl ammonium hydroxide aqueous solution dropping into 25% are in reactor, drop into again or the zinc of load calculated amount or iron or tin or plumbous or nickel or manganese or aluminium or all metal alloys such as metal simple-substance or Raney's nickel such as magnesium or copper in this reactor, control temperature-10 ~ 220 DEG C, drop into the carbonic acid gas of calculated amount or carbonate or formate or formaldehyde or bicarbonate of ammonia or urea or acetic acid, retain certain reaction times, the principal product generated is the alcohol mixture of oxyacetic acid or ethylene glycol+ethanol+methyl alcohol or the alcohol mixture of glycine or quadrol or ethanol+butyleneglycol, simultaneously coproduct hydrogen potassium oxide or sodium hydroxide or lithium hydroxide or calcium hydroxide.
7. sodium carbonate or salt of wormwood or sodium formiate or potassium formiate or carbonic acid gas are as the purposes of Material synthesis oxyacetic acid and ethylene glycol coproduct hydrogen sodium oxide or potassium hydroxide simultaneously.
8. water closes the method for hydrazine as hydrogen source reduction nitrogen peroxide synthetic ammonia G&W, comprises several steps of following order:
Select conventional interval type or flow reactor, drop into the potassium hydroxide of 30 ~ 48% of calculated amount or sodium hydroxide or lithium hydroxide or calcium hydroxide aqueous solution or aqeous suspension; Or all the alkaline aqueous solution such as the tetra-alkyl ammonium hydroxide aqueous solution dropping into 25% are in reactor, drop into again or the zinc powder of load calculated amount or the metal such as iron powder or Raney's nickel in this reactor, start and stir, control temperature-10 ~ 150 DEG C, add nitrogen peroxide or the nitrogen tetroxide of calculated amount, insulation reaction certain hour, generates ammonia and hydrazine hydrate.
9., in the environment of melting highly basic, carbonic acid gas or nitrogen peroxide or sulfurous gas prepare the method for carbon simple substance or nitrogen or sulphur simple substance as raw material single step reaction, comprise several steps of following order:
Select conventional stirred reactor, drop into calculated amount without water sodium hydroxide or anhydrous potassium hydroxide or their mixture in this reactor, start and stir, control temperature 180 ~ 800 DEG C, add the carbonic acid gas of calculated amount or nitrogen peroxide or sulfurous gas, insulation reaction certain hour, Formed simple substance or nitrogen or sulphur simple substance.
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| CN107151238A (en) * | 2016-03-05 | 2017-09-12 | 李坚 | Formates or method and application that carbonate is Material synthesis glycolide and glycolic acid oligomer |
| CN107176943A (en) * | 2016-03-10 | 2017-09-19 | 李坚 | Formates is method and the application of Material synthesis glycolaldehyde dimer and its derivative |
| CN107266412A (en) * | 2016-04-09 | 2017-10-20 | 李坚 | CO2Or carbonate or formates and water are method and the application that raw material prepares the cyclic ethers such as metaformaldehyde |
| CN109022782A (en) * | 2018-09-27 | 2018-12-18 | 武汉工程大学 | The method for manufacturing metallic aluminium as raw material single step reaction using aluminium hydroxide |
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