CN107011135A - A kind of method that material low with content of formaldehyde prepares concentrated formaldehyde - Google Patents
A kind of method that material low with content of formaldehyde prepares concentrated formaldehyde Download PDFInfo
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- CN107011135A CN107011135A CN201710295077.XA CN201710295077A CN107011135A CN 107011135 A CN107011135 A CN 107011135A CN 201710295077 A CN201710295077 A CN 201710295077A CN 107011135 A CN107011135 A CN 107011135A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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Abstract
The present invention relates to a kind of method that material low with content of formaldehyde prepares concentrated formaldehyde, comprise the following steps：(1) methanol is added in the low material of content of formaldehyde, is reacted under the catalytic action of heteropolyacid catalyst, obtain dimethoxym ethane；(2) dimethoxym ethane obtained by step (1) carries out catalytic oxidation, obtains including the product of concentrated formaldehyde.The rate of recovery of formaldehyde in the concentrated formaldehyde product that concentration is 65~66wt%, whole technique is finally given more than 97%.It is cost-effective and the method for the invention does not need dilute formaldehyde to be directly condensed into the special equipment of concentrated formaldehyde, reduce energy consumption；The circulation of dilute formaldehyde in a device is realized, independent of production byproduct dimethoxym ethane or methenamine etc., the COD level and cost for wastewater treatment of waste water is reduced.
Description
Technical field
The present invention relates to chemical production technical field, more particularly to formaldehyde, polymethoxy dimethyl ether, polyformaldehyde, gas first
The preparation field of aldehyde and glyphosate, and in particular to a kind of method that material low with content of formaldehyde prepares concentrated formaldehyde.
Background technology
Paraformaldehyde is produced using formaldehyde as primary raw material, and solid formaldehyde is obtained by evaporation, concentration, through catalyzing and condensing, then
Vacuum dried finished product.But during paraformaldehyde is produced, formaldehyde is by concentration and extracts, and has substantial amounts of dilute first
Aldehyde is produced, and how to handle dilute formaldehyde, has become the problem of paraformaldehyde manufacturer, is handled dilute formaldehyde and is provided in existing document
In material, most published methods are only the angle from environmental protection, and formaldehyde is converted into environment permission using chemical transformation
The material of discharge, or with the method for biochemical treatment, there are shortcomings in the dilute formaldehyde of these methods processing：Conversion is incomplete,
Due to the generation of side reaction, further conversion exists part formaldehyde in the form of formaldehyde and formates, therefore after conversion processing
Solution can not be discharged directly；Formaldehyde is converted to formose class, it is impossible to recycling, causes the wasting of resources.Currently exist
In formaldehyde downstream product production process, what these dilute formalins had is concentrated again, and energy cost and investment are high, and what is had is dilute
Formaldehyde add concentrated formaldehyde in be exchanged into commodity formaldehyde sale, but because market capacity is limited or the requirement of market PARA FORMALDEHYDE PRILLS(91,95) is higher can not
It is fully utilized, the dilute formaldehyde having is further processed into methenamine or dimethoxym ethane (also known as formal, or dimethoxy
Methane), but because market is limited, economy is bad, causes this partial material to have no idea to be handled well, so that whole
Individual downstream process is not smooth.Dimethoxym ethane is originally used for gasoline addition, and market orientation instructs those skilled in the art to abandon to be contracted with first
The less expensive formaldehyde of aldehyde production prices, after requirement must not add dimethoxym ethane in gasoline national standard, the city of dimethoxym ethane
Field flow is dynamic to be deteriorated, sluggish market.
As reaction raw materials formaldehyde more than the conventional method that is aoxidized by methanol prepare, due to reaction during form substantial amounts of
Water and make the utilization rate of methanol low.Thus the Cmax of the formalin prepared only 55wt%, will obtain higher dense
Degree is difficult.It is being that reaction raw materials prepare polyacetal resin, formaldehyde resin, phenolic resin, paraformaldehyde, urea with formaldehyde
During compound, it is desirable to which the concentration of formaldehyde is as high as possible.In order to improve the concentration of formaldehyde, prior art includes distillation or washed, or will
Formaldehyde and alcohol reaction generation hemiacetal, because concentration is not high enough, then must obtain formaldehyde enriched gas by heating evaporation, this
Cross the consersion unit of range request quite strict reaction condition, in addition it is also necessary to substantial amounts of energy consumption.
CN102329407A disclose it is a kind of produce paraformaldehyde be produce dilute formaldehyde circulation use technology, pass through thing
The means of reason break the change between the compound between methanol-formaldehyde in formaldehyde waste water, methanol-water and Formaldehyde-water-derivative
Interaction and chemical balance relation, realizes the separation of formaldehyde and water, but formaldehyde is oxidizable in concentration process produces
Formic acid concn, workshop section produces after the yield of reduction formaldehyde not only influences, and production steady in a long-term is also hidden some dangers for, etching apparatus is tight
Weight, maintenance of equipment expends big.Therefore, find it is a kind of do not need special equipment can Efficient Cycle it is high pervasive using dilute formaldehyde
The method of resource of property has great importance.
The content of the invention
In view of problems of the prior art, an object of the present invention is to provide a kind of thing low with content of formaldehyde
The method that material prepares concentrated formaldehyde, comprises the following steps：
(1) methanol is added in the low material of content of formaldehyde, is reacted under the catalytic action of heteropolyacid catalyst, obtain first
Acetal；
(2) dimethoxym ethane obtained by step (1) carries out catalytic oxidation, obtains including the product of concentrated formaldehyde.
The low material of step (1) the of the present invention content of formaldehyde is production in the middle of being produced in formaldehyde downstream product production process
Thing.
Preferably, the formaldehyde downstream product includes metaformaldehyde, polyformaldehyde, polymethoxy dimethyl ether (DMMn) or gaseous state
In formaldehyde any one or at least two combination, wherein, it is typical but non-limiting to be combined as：Metaformaldehyde and polyformaldehyde
Combination, paraformaldehyde and gaseous formaldehyde, the combination of DMMn and gaseous formaldehyde.
Preferably, in the low material of step (1) described content of formaldehyde formaldehyde concentration be 5~25wt%, such as 5wt%,
8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 23wt% or 25wt% etc., preferably 10~20wt%.
Step (1) the of the present invention heteropolyacid catalyst preferably includes phosphotungstic acid catalyst.
Preferably, the heteropolyacid catalyst includes carried phospho-tungstic acid catalyst, and the carrier includes SnO, ZrO2Or
SiO2In any one or at least two combination, wherein, it is typical but non-limiting to be combined as：SnO and ZrO2Combination,
SnO and SiO2Combination, ZrO2And SiO2Combination, preferably SnO and/or ZrO2。
Preferably, the carrier also includes Al2O3, preferably γ-Al2O3.Addition and the stronger Al of heteropoly acid active force2O3Energy
Solution-off of the carried heteropoly acid catalyst in reaction solution is adjusted, reaction efficiency is further improved.
Preferably, the specific surface area of the carrier is more than or equal to 100m2/ g, such as 100m2/g、130m2/g、180m2/g、
200m2/g、220m2/g、250m2/g、280m2/g、300m2/g、330m2/ g or 350m2/ g etc., preferably 200~350m2/g.Compare table
Area increase contributes to contact of the reactant with catalyst, but the excessive carrier of specific surface area there may be more narrow and small hole
Footpath is unfavorable for separating for diffusion of the reactant in duct and catalyst and product.
Preferably, the carrier is hollow ball meso-hole structure.The appropriate duct of structure offer and absorption property, contribute to
Catalytic activity is improved, while it is easy to the separation of catalyst and product, so that yield is improved, catalyst reusable edible.
Preferably, in the carried phospho-tungstic acid catalyst carrier with load phosphotungstic acid catalyst mass ratio for (1~
10):1, such as 1:1、1.5:1、2:1、2.3:1、2.5:1、2.8:1、3:1、3.4:1、3.7:1、4:1、4.2:1、4.5:1、
4.8:1、5:1、5.3:1、5.5:1、5.7:1 or 6:1 etc., preferably (2.5~6):1.Excellent catalytic activity can be obtained and subtracted
The addition of few catalyst, it is cost-effective.
Preferably, the preparation method of the carried phospho-tungstic acid catalyst includes infusion process.
Preferably, the preparation method of the carried phospho-tungstic acid catalyst comprises the following steps：By the carrier in phosphorus tungsten
In acid solution in 40~100 DEG C impregnate 6~72h, such as dipping temperature of the described carrier in Salkowski's solution be 40 DEG C, 45
DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 64 DEG C, 70 DEG C, 76 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C etc., dip time be 6h,
8h, 12h, 18,20h, 24h, 30h, 36h, 45h, 60h, 68h or 72h etc..
Preferably, the carrier is impregnated into 12~36h in Salkowski's solution in 50~80 DEG C.
Preferably, the Salkowski's solution Salkowski's solution is the mixed solution of n-butanol and phosphotungstic acid.
Preferably, the mol ratio of carrier, n-butanol and phosphotungstic acid is 1 in the dipping process:(20~40):(0.01~
0.5), such as 1:20:0.01、1:40:0.01、1:40:0.5、1:30:0.1 or 1:25:0.2 etc., preferably 1:(20~30):
(0.1~0.2).
The process conditions that the present invention prepares loaded catalyst are cooperateed with mutually, and method does not need the auxiliary of surfactant,
The load capacity of phosphotungstic acid is larger on carrier, and with appropriate solution-off, has extended cycle life；Will not after into catalystic converter system
The impurity of influence reaction and post processing is introduced, and preparation technology is simple, it is easy to industrialize.
Step (1) the of the present invention volume ratio for adding methanol and the low material of content of formaldehyde is preferably (0.2~0.8):
1, such as 0.2:1、0.25:1、0.3:1、0.36:1、0.4:1、0.47:1、0.5:1、0.6:1、0.7:1 or 0.8:1 etc., preferably
(0.2~0.5):1.
Preferably, the mass ratio of the heteropolyacid catalyst of step (1) described addition and the low material of content of formaldehyde is (0.5
~1.2):1, such as 0.5:1、0.58:1、0.6:1、0.7:1、0.8:1、0.9:1、11.1:1 or 1.2:1 etc., preferably (0.6~
1):1。
Preferably it is fractionated while step (1) the of the present invention reaction.It will chemically react and physical fractionation is integrated by greatly
Reaction efficiency and conversion ratio are improved greatly and energy consumption is low.
Preferably, the form of the reactant mixture of step (1) is slurry.Catalyst is worn into after microparticle or ultramicro powder
Slurry is mixed into reaction solution, stirring reaction can further improve catalytic efficiency, and the more catalyst changeout that need not stop, be not required to
Solid-liquid separation special equipment is wanted, is adapted to industrialized production.
Used catalyst is helped including iron molybdate, molybdenum trioxide and catalysis in step (2) the of the present invention catalytic oxidation
Agent.Its selectivity to dimethoxym ethane can be improved by optimizing the structure and composition of composite catalyst, conversion ratio is improved and formaldehyde is received
Rate.
The mol ratio of molybdenum element and ferro element is (1~3) in the catalyst:1, such as 1:1、1.2:1、1.5:1、1.8:
1、2:1、2.2:1、2.4:1、2.6:1、2.8:1 or 3:1 etc., preferably (1~2):1.
Preferably, the catalyst aid includes metal M1And M2Oxide, M1Including V and/or Mn, M2Including Cr, Co,
In Ni, W, Bi or alkali metal any one or at least two combination, wherein typical but non-limiting be combined as：Cr and Co
Combination, Ni and W combination, the combination of Bi and alkali metal, Cr and W combination, the combination of W and alkali metal.
Preferably, M in the catalyst1Oxide shared by mass percent be 0.1~1%, such as 0.1%,
0.2%th, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1% etc., preferably 0.1~0.4%；
Preferably, M in the catalyst2Oxide shared by mass percent be 1~20%, such as 1%, 2%,
3%th, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%
Or 20% etc., preferably 10~15%；
Preferably, the catalyst be hollow cylinder loop configuration, its external diameter 4~6mm, such as 4mm, 4.2mm,
4.5mm, 4.8mm, 5mm, 5.3mm, 5.5mm, 5.7mm or 6mm etc., 1~3mm of internal diameter, such as 1mm, 1.2mm, 1.5mm,
1.8mm, 2mm, 2.2mm, 2.4mm, 2.6mm, 2.8mm or 3mm etc., height 3~6mm, such as 3mm, 3.5mm, 3.8mm, 4mm,
4.4mm, 4.7mm, 5mm, 5.2mm, 5.5mm, 5.8mm or 6mm etc..
Preferably, the preparation process of the catalyst includes：Shaping；During the shaping add account for catalyst weight 1~
10% shaping assistant, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Preferably, the shaping assistant is molten including stearic acid, odium stearate, sesbania powder, methylcellulose, Alumina gel or silicon
In glue any one or at least two combination, wherein typical but non-limiting be combined as：Stearic acid and odium stearate
Combination, the combination of sesbania powder and methylcellulose, the preferably combination of Alumina gel and Ludox, methylcellulose and/or Alumina gel.
Partial pressure of oxygen during step (2) the of the present invention catalytic oxidation is preferably 0.2~0.5, such as 0.2,
0.25th, 0.3,0.32,0.35,0.38,0.4,0.45 or 0.5 etc. preferably 0.3~0.4.
Preferably, step (2) the catalytic oxidation temperature be 320~350 DEG C, such as 320 DEG C, 330 DEG C, 332 DEG C,
335 DEG C, 338 DEG C, 340 DEG C, 342 DEG C, 345 DEG C, 348 DEG C or 350 DEG C etc., preferably 335~345 DEG C.
Step (2) products therefrom of the present invention preferably also includes dilute formaldehyde.
Preferably, dilute formaldehyde return to step (1).Form closed cycle, synergy waste reduction.
Preferably, the concentration of concentrated formaldehyde described in step (2) be 65~66wt%, such as 65wt%, 65.1wt%,
65.2wt%, 65.3wt%, 65.4wt%, 65.5wt%, 65.6wt%, 65.7wt%, 65.8wt%, 65.9wt% or
66wt% etc..
Raw materials for production of the concentrated formaldehyde preferably directly as formaldehyde downstream product in step (2) products therefrom of the present invention.
As currently preferred technical scheme, the method for preparing concentrated formaldehyde with the low material of content of formaldehyde includes following step
Suddenly：
(1) methanol is added the concentration of formaldehyde in the low material of 5~25wt% content of formaldehyde, to be mixed into slurry shape
Formula, reacts under the catalytic action of carried phospho-tungstic acid catalyst, while being fractionated, obtains dimethoxym ethane；Wherein methanol and first
The volume ratio of the low material of aldehyde is (0.2~0.8):1, the matter of carried phospho-tungstic acid catalyst and the low material of content of formaldehyde
Amount is than being (0.5~1.2):1, the carrier of carried phospho-tungstic acid catalyst includes SnO, ZrO2Or SiO2In any one or extremely
Few two kinds combination and Al2O3, carried phospho-tungstic acid catalyst is that specific surface area is more than or equal to 100m2/ g hollow ball is mesoporous
The mass ratio of structure, the carrier and the carried phospho-tungstic acid catalyst is (1~10):1, the carried phospho-tungstic acid catalysis
The preparation method of agent includes infusion process；
(2) dimethoxym ethane obtained by step (1) is under the catalytic action of iron molybdate, molybdenum trioxide and catalyst aid, and partial pressure of oxygen is
0.2~0.5, reaction temperature obtains including concentrated formaldehyde and dilute formaldehyde to carry out catalytic oxidation under conditions of 320~350 DEG C
Product, dilute formaldehyde return to step (1), raw materials for production of the concentrated formaldehyde directly as formaldehyde downstream product.
Compared with prior art, the present invention at least has the advantages that：
The heteropolyacid catalyst used in the method for the invention has the catalytic performance of homogeneous catalyst, while not corroding
Equipment, side reaction is few, aftertreatment technology is simple, catalyst can be recycled；Combination catalyst used in catalysis oxidation has
High selectivity and catalytic activity；In the catalytic reaction for being applied to the low material of content of formaldehyde, it is 65 that can finally give concentration
The rate of recovery of formaldehyde is more than 97% in~66wt% concentrated formaldehyde product, whole technique.And the method for the invention need not
Dilute formaldehyde is directly condensed into the special equipment of concentrated formaldehyde, cost-effective, reduces energy consumption；Realize dilute formaldehyde following in a device
Ring, independent of production byproduct dimethoxym ethane or methenamine etc., reduces the COD level and cost for wastewater treatment of waste water.
Brief description of the drawings
Fig. 1 is the schematic flow sheet that the material low with content of formaldehyde of the present invention prepares the method for concentrated formaldehyde.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are defined by claims.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment is as follows, those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this
The concrete restriction of invention.
Embodiment 1
1) collect the intermediate product of production polymethoxy dimethyl ether process, the wherein concentration of formaldehyde is 5wt%, by methanol plus
Enter in the intermediate product, the volume ratio of wherein methanol and the intermediate product is 0.2:1, carried phospho-tungstic acid catalyst is added,
Slurry is made, stirring reaction obtains dimethoxym ethane；Wherein, the relevant parameter and preparation condition of catalyst agent are as shown in table 1, plus
The mass ratio for entering catalyst and intermediate product is 0.5:1；
2) partial pressure of oxygen 0.2, at 320 DEG C, by step 1) gained dimethoxym ethane iron molybdate, molybdenum trioxide and catalyst aid work
Lower catalysis oxidation is used, product is collected.The relevant parameter of the catalyst is diameter 1mm spheric granules as shown in table 2.
Comparative example 1
With differing only in for embodiment 1：Step 1) used in catalyst be the macroporous cation with sulfonate groups
Exchange membrane.
Embodiment 2
1) intermediate product of production metaformaldehyde process is collected, the wherein concentration of formaldehyde is 25wt%, and methanol is added should
In intermediate product, the volume ratio of wherein methanol and the intermediate product is 0.8:1, carried phospho-tungstic acid catalyst is added, is made
Slurry, stirring reaction obtains dimethoxym ethane；Wherein, the relevant parameter and preparation condition of catalyst agent as shown in table 1, urge by addition
The mass ratio of agent and intermediate product is 1.2:1；
2) partial pressure of oxygen 0.5, at 350 DEG C, by step 1) gained dimethoxym ethane iron molybdate, molybdenum trioxide and catalyst aid work
Lower catalysis oxidation is used, product is collected.The relevant parameter of the catalyst is diameter 2mm spheric granules as shown in table 2.
Embodiment 3
1) intermediate product of production DMMn processes is collected, the wherein concentration of formaldehyde is 10wt%, and methanol is added in the middle of this
In product, the volume ratio of wherein methanol and the intermediate product is 0.5:1, carried phospho-tungstic acid catalyst is added, slurry is made,
Stirring reaction obtains dimethoxym ethane；Wherein, the relevant parameter and preparation condition of catalyst agent as shown in table 1, add catalyst
Mass ratio with intermediate product is 0.6:1；
2) partial pressure of oxygen 0.3, at 335 DEG C, by step 1) gained dimethoxym ethane iron molybdate, molybdenum trioxide and catalyst aid work
Lower catalysis oxidation is used, product is collected.The relevant parameter of the catalyst is external diameter 5.5mm, internal diameter 2.5mm, height as shown in table 2
5mm hollow cylinder loop configuration.Dilute formaldehyde return to step (1), concentrated formaldehyde is former directly as the production of formaldehyde downstream product
Material.
Comparative example 3
With differing only in for embodiment 3：Step 2) save catalyst aid.
Embodiment 4
1) intermediate product of production gaseous formaldehyde process is collected, the wherein concentration of formaldehyde is 20wt%, and methanol is added should
In intermediate product, the volume ratio of wherein methanol and the intermediate product is 0.4:1, carried phospho-tungstic acid catalyst is added, is made
Slurry, stirring reaction obtains dimethoxym ethane；Wherein, the relevant parameter and preparation condition of catalyst agent as shown in table 1, urge by addition
The mass ratio of agent and intermediate product is 1:1；
2) partial pressure of oxygen 0.4, at 345 DEG C, by step 1) gained dimethoxym ethane iron molybdate, molybdenum trioxide and catalyst aid work
Lower catalysis oxidation is used, product is collected.The relevant parameter of the catalyst is external diameter 4mm, internal diameter 3mm, height 4mm as shown in table 2
Hollow cylinder loop configuration.Dilute formaldehyde return to step (1), raw materials for production of the concentrated formaldehyde directly as formaldehyde downstream product.
Comparative example 4
With differing only in for embodiment 4：Step 2) in all M of catalyst aid1Oxide, as shown in table 2.
Embodiment 5
1) intermediate product of production polyformaldehyde process is collected, the wherein concentration of formaldehyde is 15wt%, and methanol is added in this
Between in product, the volume ratio of wherein methanol and the intermediate product is 0.3:1, add the support type phosphorus tungsten of hollow ball meso-hole structure
Acid catalyst, is made slurry, and stirring reaction obtains dimethoxym ethane；Wherein, the relevant parameter and preparation condition of catalyst agent be such as
Shown in table 1, the mass ratio for adding catalyst and intermediate product is 0.8:1；
2) partial pressure of oxygen 0.35, at 340 DEG C, by step 1) gained dimethoxym ethane is in iron molybdate, molybdenum trioxide and catalyst aid
The lower catalysis oxidation of effect, collects product.Wherein, as shown in table 2, the catalyst is external diameter 5mm, interior to the relevant parameter of the catalyst
Footpath 2mm, height 5mm hollow cylinder loop configuration.Dilute formaldehyde return to step (1), concentrated formaldehyde is produced directly as formaldehyde downstream
The raw materials for production of product.
Comparative example 5
With differing only in for embodiment 5：Step 2) in all M of catalyst aid2Oxide, as shown in table 2.
Table 1 is the step 1 of embodiment 1~5) relevant parameter and preparation condition of used catalyst.Table 2 be embodiment 1~5 with
And the step 2 of comparative example 4~5) used catalyst composition, it is necessary to explanation be that "/" represents is combination, rather than "or"
The meaning.Table 3 is each embodiment and the rate of recovery and the concentration of concentrated formaldehyde of the final formaldehyde of comparative example.
Table 1
Table 2
Table 3
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of method that material low with content of formaldehyde prepares concentrated formaldehyde, it is characterised in that comprise the following steps：
(1) methanol is added in the low material of content of formaldehyde, reacted under the catalytic action of heteropolyacid catalyst, obtain first contracting
Aldehyde；
(2) dimethoxym ethane obtained by step (1) carries out catalytic oxidation, obtains including the product of concentrated formaldehyde.
2. the method as described in claim 1, it is characterised in that the low material of step (1) described content of formaldehyde is formaldehyde downstream
The intermediate product produced in process of producing product；
Preferably, the formaldehyde downstream product includes appointing in metaformaldehyde, polyformaldehyde, polymethoxy dimethyl ether or gaseous formaldehyde
Meaning it is a kind of or at least two combinations；
Preferably, the concentration of formaldehyde is 5~25wt%, preferably 10~20wt% in the low material of step (1) described content of formaldehyde.
3. method as claimed in claim 1 or 2, it is characterised in that step (1) described heteropolyacid catalyst is urged including phosphotungstic acid
Agent；
Preferably, the heteropolyacid catalyst includes carried phospho-tungstic acid catalyst, and the carrier includes SnO, ZrO2Or SiO2In
Any one or at least two combination, preferably SnO and/or ZrO2；
Preferably, the carrier also includes Al2O3, preferably γ-Al2O3；
Preferably, the specific surface area of the carrier is more than or equal to 100m2/ g, preferably 200~350m2/g；
Preferably, the carrier is hollow ball meso-hole structure；
Preferably, the mass ratio of carrier and the phosphotungstic acid catalyst of load is (1~10) in the carried phospho-tungstic acid catalyst:
1, preferably (2.5~6):1；
Preferably, the preparation method of the carried phospho-tungstic acid catalyst includes infusion process；
Preferably, the preparation method of the carried phospho-tungstic acid catalyst comprises the following steps：The carrier is molten in phosphotungstic acid
In liquid 6~72h is impregnated in 40~100 DEG C；
Preferably, the carrier is impregnated into 12~36h in Salkowski's solution in 50~80 DEG C；
Preferably, the Salkowski's solution Salkowski's solution is the mixed solution of n-butanol and phosphotungstic acid；
Preferably, the mol ratio of carrier, n-butanol and phosphotungstic acid is 1 in the dipping process:(20~40):(0.01~0.5),
It is preferred that 1:(20~30):(0.1~0.2).
4. the method as described in any one of claims 1 to 3, it is characterised in that step (1) is described to add methanol and content of formaldehyde
The volume ratio of low material is (0.2~0.8):1, preferably (0.2~0.5):1；
Preferably, the mass ratio of the heteropolyacid catalyst of step (1) described addition and the low material of content of formaldehyde for (0.5~
1.2):1, preferably (0.6~1):1.
5. the method as described in any one of Claims 1 to 4, it is characterised in that divided while step (1) described reaction
Evaporate；
Preferably, the form of the reactant mixture of step (1) is slurry.
6. the method as described in any one of Claims 1 to 5, it is characterised in that used in step (2) described catalytic oxidation
Catalyst includes iron molybdate, molybdenum trioxide and catalyst aid, in the catalyst mol ratio of molybdenum element and ferro element for (1~
3):1, preferably (1~2):1；
Preferably, the catalyst aid includes metal M1And M2Oxide, M1Including V and/or Mn, M2Including Cr, Co, Ni, W,
In Bi or alkali metal any one or at least two combination；
Preferably, M in the catalyst1Oxide shared by mass percent be 0.1~1%, preferably 0.1~0.4%；
Preferably, M in the catalyst2Oxide shared by mass percent be 1~20%, preferably 10~15%；
Preferably, the catalyst is hollow cylinder loop configuration, its external diameter 4~6mm, 1~3mm of internal diameter, 3~6mm of height；
Preferably, the preparation process of the catalyst includes：Shaping；Added during the shaping and account for catalyst weight 1~10%
Shaping assistant；
Preferably, the shaping assistant is included in stearic acid, odium stearate, sesbania powder, methylcellulose, Alumina gel or Ludox
Any one or at least two combination, preferably methylcellulose and/or Alumina gel.
7. the method as described in any one of claim 1~6, it is characterised in that during step (2) described catalytic oxidation
Partial pressure of oxygen be 0.2~0.5, preferably 0.3~0.4；
Preferably, catalytic oxidation temperature is 320~350 DEG C, preferably 335~345 DEG C in step (2).
8. the method as described in any one of claim 1~7, it is characterised in that step (2) products therefrom also includes dilute formaldehyde；
Preferably, dilute formaldehyde return to step (1)；
Preferably, the concentration of concentrated formaldehyde described in step (2) is 65~66wt%.
9. the method as described in any one of claim 1~8, it is characterised in that the concentrated formaldehyde in step (2) products therefrom is direct
It is used as the raw materials for production of formaldehyde downstream product.
10. the method as described in any one of claim 1~9, it is characterised in that comprise the following steps：
(1) methanol is added into the concentration of formaldehyde in the low material of 5~25wt% content of formaldehyde, to be mixed into slurry form,
Reacted under the catalytic action of carried phospho-tungstic acid catalyst, while being fractionated, obtain dimethoxym ethane；Wherein methanol and content of formaldehyde
The volume ratio of low material is (0.2~0.8):1, the mass ratio of the carried phospho-tungstic acid catalyst material low with content of formaldehyde is
(0.5~1.2):1, the carrier of carried phospho-tungstic acid catalyst includes SnO, ZrO2Or SiO2In any one or at least two
Combination and Al2O3, carried phospho-tungstic acid catalyst is that specific surface area is more than or equal to 100m2/ g hollow ball meso-hole structure, institute
The mass ratio for stating carrier and the carried phospho-tungstic acid catalyst is (1~10):1, the system of the carried phospho-tungstic acid catalyst
Preparation Method includes infusion process；
(2) dimethoxym ethane obtained by step (1) is under the catalytic action of iron molybdate, molybdenum trioxide and catalyst aid, and partial pressure of oxygen is 0.2~
0.5, reaction temperature obtains including the production of concentrated formaldehyde and dilute formaldehyde to carry out catalytic oxidation under conditions of 320~350 DEG C
Thing, dilute formaldehyde return to step (1), raw materials for production of the concentrated formaldehyde directly as formaldehyde downstream product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036755A (en) * | 1988-02-03 | 1989-11-01 | 旭化成工业株式会社 | The method for preparing formaldehyde and derivative thereof |
| CN1978052A (en) * | 2005-12-07 | 2007-06-13 | 南化集团研究院 | Iron-molybdic catalyst for preparing concentrated formaldehyde by formal oxidation and preparing method |
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2017
- 2017-04-28 CN CN201710295077.XA patent/CN107011135A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036755A (en) * | 1988-02-03 | 1989-11-01 | 旭化成工业株式会社 | The method for preparing formaldehyde and derivative thereof |
| EP0327343A3 (en) * | 1988-02-03 | 1991-05-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing formaldehyde and derivatives thereof |
| CN1978052A (en) * | 2005-12-07 | 2007-06-13 | 南化集团研究院 | Iron-molybdic catalyst for preparing concentrated formaldehyde by formal oxidation and preparing method |
Non-Patent Citations (1)
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| 金明善 等: "改性杂多酸催化剂的制备及其在甲缩醛合成中的催化活性", 《复旦学报（自然科学版）》 * |
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