CN101348425A - Method for coproduction of chrome tanning agent and menadione - Google Patents

Abstract

The invention discloses the production of menadione, in particular disclosing a method for manufacturing menadione through combining with a chrome tanning agent. The method is characterized in that the method comprises the following (1) a step of preparing menadione, during which, methylnaphthalene, water and EL series emulsifying agents are added in a first reaction bulb; moreover, sodium bichromade and water are added in a second reaction bulb, and concentrated sulfuric acid is added slowly while stirring for cooling down; then prepared red liquor is slowly dripped into the first reaction bulb while stirring, and is filtered and dried so as to obtain bright yellow crystallized menadione powder; and (2) a step of preparing basic chrome sulphate, during which, the mother liquor obtained during preparing menadione is taken out, and sodium bichromade and dextrose solution are added in order; and chrome tanning agent basic chrome sulphate is obtained after spray drying. Through adopting a chrome tanning agent basic chrome sulphate production device to carry out joint production for menadione, the method realizes maximization of resource utilization; moreover, the method greatly reduces production cost for both sides and the release of waste liquids.

Description

Method with chrome tanning agent coproduction production vitamin k4

(1) technical field

The present invention relates to a kind of production of vitamin k4, particularly a kind of method of producing vitamin k4 with the chrome tanning agent coproduction.

(2) background technology

The derivative of vitamin k4 is a vitamin K, and vitamin k4 is applied to the synthetic of vitamin K, and vitamin K is converted into vitamin k4 again, in vivo so the application of vitamin k4 is the application of vitamin K after being absorbed by animal.

Vitamin K is the derivative of vitamin k4, has another name called vitamin K or antihemorrhagic vitamin, is to form necessary kind of VITAMIN of thrombogen in the animal body.The vitamin K that nature exists has two classes: the phylloquinone that exists in the green plants is called vitamin K ₁, another kind of by reaching other microorganism synthetic menaquinones in the animal intestine, be called vitamin K ₂Synthetic vitamin K arranged ₃, K ₄Vitamin K ₁Also can manually synthesize.Vitamin K ₃Active high, belongs to water-solublely, easy to use, so be most widely used.The major physiological function of vitamin K is to promote the synthetic zymoplasm of liver and proconvertin, IX X, and plays activation, participates in coagulation process.The animal K that is deficient in vitamin can cause internal hemorrhage, wound cruor time extending or bleed more than.Except that Blood clotting, it is reported that vitamin K dependent protein matter and peptide participate in calcium metabolism.Generally speaking, because the certain micro-organisms of animal digestive tract can synthesize enough vitamin Ks ₂, adult animals is difficult for lacking.Young animal, particularly cage bird can not be by synthesise vitamins K ₂Satisfy the demand, in addition, when intestinal tract disease or animal were taken Broad spectrum antibiotics and antibacterial medicine preparation for a long time, the enteric microorganism vigor descended, and can cause vitamin K deficiency; Utilization ratio by the temparin reduction vitamin K that forms in the septic plant feed contains this thing and is added with sulfonamides in feed, during microbiotic, need to increase daily ration vitamin K content.Vitamin K is easily destroyed by light and alkali, should keep in Dark Place.

The external country that produces vitamin k4 mainly contains Italy, Germany, Switzerland, the U.S., Japan etc.The main technique route is divided into vapour phase oxidation process and liquid phase oxidation.Vapour phase oxidation process is with V ₂O ₅Be catalyzer, beta-methylnaphthalene carries out oxidation with warm air under gaseous state.These method characteristics are that production cost is low, but continuous production, throughput is big, and no waste liquid produces, but because oxidizing temperature is higher, the oxidation side reaction of the degree of depth takes place easily, 2-methyl 1, the yield of 4-naphthoquinones is lower.On data, do not see industrialized report as yet.Domestic enterprise once carried out this research, but, impurity low because of yield interrupts more.Vitamin K in the world at present ₃Production adopt liquid phase oxidation mostly, this method can be divided into 3 kinds again by the difference of used oxygenant.

1) hydrogen peroxide oxidation process

In the presence of the palladium polystyrene sulfonic acid resin, use hydrogen peroxide oxidation beta-methylnaphthalene (NQ), get 2 methyl 1, the 4-naphthoquinones, the transformation efficiency of its beta-methylnaphthalene is 96%, β-vitamin k4 is 65% to the yield of beta-methylnaphthalene, but palladium compound needs regeneration in the reaction, and amount of industrial wastewater is bigger, if control the bad danger that also has blast in the reaction process.Therefore, the industrialized difficulty of hydrogen peroxide oxidation process is bigger.

2) cerium salt oxidation style

Skarzewski has reported the novel process of making oxygenant with cerous sulfate salt.With cerous sulfate salt oxidation beta-methylnaphthalene, waste liquid is through electrolytic regeneration then, and 2-methyl 1, the yield of 4-naphthoquinones are 25%～65%.But less because of cerium salt resource, cost an arm and a leg, thereby limited the development of this technology.

3) chromic salts oxidation style

Whole world vitamin K ₃This method that adopts more than 90% of output is produced.This method is with Cr ⁶⁺(comprising sodium dichromate and chromic trioxide etc.) makes oxygenant, according to the treatment process difference of raffinate after the oxidation, is divided into electrolysis process and joint process again.

Electrolysis process: electrolysis process is used chromic acid solution oxidation beta-methylnaphthalene under 40 ℃, strong mixing condition exactly, 2-methyl 1, the 4-naphthoquinones.Its oxidation raffinate (mainly contains Cr ³⁺And acid) flow into electrolyzer, make Cr through electrolysis ³⁺Lose 3 electronics at anode and become Cr6+, Cr6+ is the deoxidation beta-methylnaphthalene again, and the oxidation raffinate recycles through electrolytic regeneration, does not produce any waste.The external lab scale report of only seeing electrolysis process.China is the country with electrolysis explained hereafter vitamin K3 output maximum.The characteristics of this technology are that oxygenant recycles, and flow process is short, stable operation, and β-vitamin k4 quality is good.Electrolysis process is the rational operational path of technological sciences beyond doubt, and shortcoming is that one-time investment is big, is difficult to enlarge output.

(3) summary of the invention

The present invention is in order to remedy the deficiencies in the prior art, provides a kind of cost low, the maximized method of producing vitamin k4 with the chrome tanning agent coproduction that utilize resource.

The present invention is achieved through the following technical solutions:

A kind of method of producing vitamin k4 with the chrome tanning agent coproduction, its special character is: comprise the steps:

(1) preparation of vitamin k4: the 10g methylnaphthalene, 30～60g water and 0.3～0.4gEL series emulsifying agent add in 500ml first reaction flask, fully stir mixed down at 40 ℃; In 40-80g sodium dichromate and 80～120ml water adding 500ml, second reaction flask,, be cooled to 40 ℃ and get red liquid in addition stirring slow 60～100 gram vitriol oils that add under the cooling condition, stand-by; Then the red liquid for preparing slowly is added drop-wise in first reaction flask under stirring condition, maintains the temperature at 37-50 ℃, drip to finish and slowly to be warming up to 55-75 ℃, reacted 0.5 hour, be cooled to 40-45 ℃ then, filtering drying gets glassy yellow crystallinity vitamin k4 powder;

(2) preparation of basic chromium sulfate: get the mother liquid obtained 200ml of preparation vitamin k4 and record unreacted Na ₂Cr ₂O ₇2H ₂O m gram/L, unreacted sulfuric acid n gram/L, place the 500ml reaction flask then, add 0.2* (n-m) gram sodium dichromate, fully stir, be warmed up to 100 ℃ then and slowly add the glucose solution that includes 0.04* (n-m) gram glucose, finish and keep reaction 1 hour, spraying drying gets the chrome tanning agent basic chromium sulfate.

The used EL series of the present invention emulsifying agent is the product of Hai'an, Jiangsu petroleum chemical plant public offering on market as catalyzer, and its chemical ingredients is: Viscotrol C/hydrogenated castor oil and ethylene oxide condensate.The present invention mainly uses EL-10, EL-12, EL-20, the HEL-20 specification in the EL series emulsifying agent.

Characteristics of the present invention:

(1) The Study on New Technology

Joint process: this process using sodium dichromate, chromic trioxide etc. (are Cr ⁶⁺) as oxygenant, the oxidation beta-methylnaphthalene, its oxidation raffinate is made the chrome tanning agent that leather industry is used through modulation.Joint process is state-of-the-art in the world technology, and the present invention just adopts this technology.The characteristics of this technology are less investment, instant effect, the discharge of good in economic efficiency, no waste liquid.This technology operates steadily, the vitamin K that the vitamin k4 that obtains is produced ₃And the chromium powder quality has all reached the quality standard of national corresponding product.Facts have proved the vitamin k4 production technique that joint process is a less investment, instant effect, cost is low.

(2) selection of catalysts:

During the methylnaphthalene oxidation, 2-methyl 1,4-naphthoquinones are not unique products, product that neither be final.Generally include following principal reaction during the beta-methylnaphthalene oxidation: wherein vitamin k4, phthalic anhydride, MALEIC ANHYDRIDE also may further be oxidized to corresponding oxide compound.Therefore, select suitable catalyzer particularly important.

The applicant adopts traditional technology to produce vitamin k4 before 2006, multiple starting material such as main raw material(s) Ortho Toluidine, Manganse Dioxide, chromic anhydride, acetic acid, toluene, ethanol.But afterwards because starting material such as Manganse Dioxide are very in short supply and price sharp rises, it is longer to add technical process, and liquid and waste slag produced aftertreatment amount is bigger, and difficulty reaches large-scale production.For this reason, the end of the year 2005 are under the scientific and technical personnel's of company effort, by consulting document and a large amount of experiments, on technology, improve, simultaneously again according to new technology, we carry out coordinated production with Jinanyuxing Chemical General Factory, the Yellow River, Inner Mongol chromium salt factory respectively, have realized the important breakthrough that vitamin k4 is produced.By the reform of this technology, vitamin k4 manufacturing enterprise and chromium powder factory are complemented one another, each takes what he needs, and in coproduction, we provide beta-methylnaphthalene, allow chromium powder factory save reductive agent sugar (or SO ₂), and we utilize their mother liquor to make my company save sodium dichromate and sulfuric acid cost.Both sides are all lower greatly like this production cost meets the circular economy concept and the principle of reciprocity and mutual benefit very much.The innovation of this technology makes the production cost of K3 per ton reduce by 20,000 yuan, after project is built up, and 1.2 ten thousand tons in year saving manganese ore powder, 1000 tons of divinyl reclaim 3000 tons of chromic salts, reduce 30,000 tons of discharging of waste liquid.

What the vitamin k4 that the present invention at present produces adopted is the production technique that technology content is the highest in the world, production cost is minimum, quality product is optimum.Utilize chrome tanning agent basic chromium sulfate production equipment, behind the combination producing vitamin k4, make utilization of resources maximization, both sides all greatly reduce production cost, have reduced discharging of waste liquid, are the successful models of resources conservation and comprehensive utilization.

(4) embodiment

Embodiment 1:

This preparation technology is as follows:

1. the preparation of vitamin k4

10g methylnaphthalene (content＞95%), 35g water and 0.35gEL series emulsifying agent add in the 500ml reaction flask, fully stir mixed down at 40 ℃.In addition 40g sodium dichromate (content＞98%) and 85ml water are added in another 500ml reaction flask, slowly add the 60g vitriol oil under the cooling condition stirring, be cooled to 40 ℃ " red liquid " is stand-by; Then the red liquid for preparing slowly is added drop-wise in first reaction flask under stirring condition, maintains the temperature at 48 ℃, drip the complete 70 ℃ of reactions 0.5 hour that slowly are warming up to, be cooled to 45 ℃ then, filtering drying gets glassy yellow crystallinity powder 6.5g, measure content 91.1%, yield 48%.

2. the preparation of basic chromium sulfate

Get the mother liquid obtained 200ml of preparation vitamin k4 and record unreacted Na ₂Cr ₂O ₇2H ₂O 17 gram/L, unreacted sulfuric acid 22 gram/L, place the 500ml reaction flask then, add 5 gram sodium dichromates, fully stir, be warmed up to 100 ℃ then and slowly add and include 1 gram glucose solution, finish and keep reaction 1 hour, spraying drying gets basic chromium sulfate, records Cr203 content 24.8%, basicity 33.0%.

Embodiment 2:

This preparation technology is as follows:

(1) preparation of vitamin k4: the 10g methylnaphthalene, 55g water and 0.38gEL series emulsifying agent add in 500ml first reaction flask, fully stir mixed down at 40 ℃; In 75g sodium dichromate and 110ml water adding 500ml second reaction flask,, be cooled to 40 ℃ and get red liquid in addition stirring slow 105 grams, 98% sulfuric acid that adds under the cooling condition, stand-by; Then the red liquid for preparing slowly is added drop-wise in first reaction flask under stirring condition, maintains the temperature at 43 ℃, drip to finish and slowly to be warming up to 60 ℃, reacted 0.5 hour, and be cooled to 42 ℃ then, filtering drying, get glassy yellow crystallinity vitamin k4 powder 7.5g, measure content 97.2%, yield 59%.；

(2) preparation of basic chromium sulfate: get the mother liquid obtained 200ml of preparation vitamin k4 and record unreacted Na ₂Cr ₂O ₇2H ₂O 23 gram/L, unreacted sulfuric acid 31 gram/L, place the 500ml reaction flask then, add 7.6 gram sodium dichromates, fully stir, be warmed up to 100 ℃ then and slowly add the glucose solution that includes 1.5 gram glucose, finish and keep reaction 1 hour, spraying drying gets the chrome tanning agent basic chromium sulfate, records Cr2O3 content 25.1%, basicity 32.7%.

Claims (1)

1. a method of producing vitamin k4 with the chrome tanning agent coproduction is characterized in that: comprise the steps:

(1) preparation of vitamin k4: the 10g methylnaphthalene, 30～60g water and 0.3～0.4gEL series emulsifying agent add in 500ml first reaction flask, fully stir mixed down at 40 ℃; In 40g-80g sodium dichromate and 80～120ml water adding 500ml, second reaction flask,, be cooled to 40 ℃ and get red liquid in addition stirring slow 60～120 gram vitriol oils that add under the cooling condition, stand-by; Then the red liquid for preparing slowly is added drop-wise in first reaction flask under stirring condition, maintains the temperature at 37-50 ℃, drip to finish and slowly to be warming up to 55-75 ℃, reacted 0.5 hour, be cooled to 40-45 ℃ then, filtering drying gets glassy yellow crystallinity vitamin k4 powder;

(2) preparation of basic chromium sulfate: get the mother liquid obtained 200ml of preparation vitamin k4 and record unreacted Na ₂Cr ₂O ₇2H ₂O m gram/L, unreacted sulfuric acid n gram/L, place the 500ml reaction flask then, add 0.2* (n-m) gram sodium dichromate, fully stir, be warmed up to 100 ℃ then and slowly add the glucose solution that includes 0.04* (n-m) gram glucose, finish and keep reaction 1 hour, spraying drying gets the chrome tanning agent basic chromium sulfate.