JPS6015670B2 - Plant medium adjustment method - Google Patents

Description

[Detailed description of the invention] TECHNICAL FIELD The present invention relates to a method for adjusting plant soil.

The present inventor has been researching phosphonitrile compounds for some time, and found that a certain structure of these compounds has degradability, and this decomposition property makes it possible to use this compound as an industrial material. It turned out to be a drawback when using it, but this property can be used to the contrary, and
The present invention was completed based on another study, that is, research on flocculants.

Organic polymer flocculants having a primary mirror containing carbon atoms are well known and currently widely used.

The present inventors have discovered a polymer flocculant having a phosphorus-nitrogen main chain that is substantially different from the known polymer flocculants having a carbon-based primary mirror. This product belongs to the so-called phosphonitrile-based (PN-based) polymer, and has the general formula (where R1, R2, R3, and R4 are cation-containing groups, anion-containing groups, hydrogen-bonding groups, halogen or inert organic group, provided that R1, R2, R3, R4
at least one of which is a cation-containing group, an anion-containing group, or a hydrogen-bonding group.

This phosphonitrile polymer differs not only in the type of main chain atoms from the above-mentioned known organic flocculants, but also has the following unique advantages. In other words, the unique feature of this PN-based polymer flocculant is that it gradually decomposes in a liquid, especially water, or in a humidifier, and converts into simple low-molecular weight compounds such as phosphoric acid, ammonium phosphate, and other phosphates. , these decomposition products serve as a nutritional source for microorganisms.

However, the decomposition rate at this time is quite slow, and can be made comparable to the decomposition (corrosion) rate of wood and dried grass in wet soil. This decomposition is mainly due to hydrolysis of the PN main chain, but decomposition of the PN main chain by microorganisms, that is, biochemical decomposition can also occur.

Additionally, both chemical (hydrolysis) and biochemical degradation may occur. Another one of this PN polymer flocculant
The major advantage of the main chain is that the main chain essentially stretches like a bran in the liquid due to the mutual repulsion of the atoms forming the main chain (P and N), and as a result, the active groups attached to the main chain are extremely active. Effective contact with suspended particles in water or lacquer particles.

On the other hand, conventional polymer flocculants generally exist largely bent in the liquid, that is, in the form of a "string", and therefore the active groups present in the center of this "string" do not work effectively. For reference, the state of existence of the above two types of polymers in liquid is schematically shown. Therefore, the present invention is characterized in that a flocculation product obtained by performing a solid-liquid separation operation using a phosphonitrile polymer having the above general formula as a flocculant is used as a soil or soil conditioner. The present invention relates to a method for adjusting a shield culture medium.

Sludge, activated sludge, etc. produced by coagulation-sedimentation methods or biological treatment methods have traditionally been incinerated, landfilled, or dumped into the ocean, but recently, efforts have been made to effectively utilize them as useful resources. There is.

That is, it is used as an organic fertilizer or a grain improver. In the coagulation-sedimentation method, the sediment (sludge) obtained by using a coagulation-sedimentation agent and the surplus activated sludge produced by the biological treatment method have a high moisture content, so they must be treated by filtration, drying, etc. Although it is made into a form that is easy to handle, a furnace filtration accelerator is used to promote dehydration in the furnace filtration process.

It has been recognized that the known flocculants, furnace filtration accelerators, etc. used remain without separation and cause soil contamination, causing various problems. In contrast, by using the above-mentioned phosphonitrile polymer as a flocculating sedimentation agent or a furnace accelerating agent according to the present invention, it not only exhibits the effects of coagulating sedimentation and accelerating furnace accelerating, but also decomposes at a certain point. It has the characteristics of being a fertilizer component like phosphorus and ammonium compounds. In other words, this flocculant remains adsorbed in the condensate after flocculation operation or furnace filtration operation, and when the condensate is stored or buried in the soil, the flocculant gradually decomposes and improves soil fertility. It is useful for In contrast, conventional synthetic organic polymer flocculants with carbon primary mirrors are difficult to decompose in the soil, are not useful for soil fertilization, and may even cause pollution problems if they remain in the soil. . This PN-based polymer flocculant can be made into various types of flocculants by changing the type of side chain, that is, it can be a cationic flocculant, an anionic flocculant, a nonionic flocculant, or an amphoteric flocculant. However, in this respect, it is almost the same as in the case of known organic polymer flocculants having a carbon primary mirror.

For example, as a side chain, an amine group, a quaternary ammonium group,
PN polymers having imine groups, etc. are cationic flocculants, and PN polymers having carboxyl groups, carboxylate groups, etc.
N-type polymers are anionic flocculants, PN-type polymers having hydroxyl groups, acrylamide groups, methacrylamide groups, etc. are /ionic flocculants, and PN-type polymers having amino acid groups, etc. are amphoteric flocculants.

These PN-based polymers are represented by the following formula, for example.

In the above formula, R is an organic group, Rc■ is a cation-containing group, R
^e represents an anion-containing group. n is a considerably large number, as in the case of a known polymer flocculant having a carbon-based primary mirror. In the case of the above-mentioned known polymer flocculants, the molecular weight is generally described in literature 2 instead of the value of n, so
In the present invention, the molecular weight of the PN polymer is generally 100,000 or more, preferably 300,000 to 300,000.
10,000 or more (see reference examples below). Note that in the above formula, the description of the three-way partner ion of each ion is omitted to simplify the description. In addition to flocculants having a structure in which cationic groups, anionic groups, /ionic groups, etc., which are original active groups, are individually bonded, flocculants having a combination of cationic groups or anionic groups and nonionic groups, and cationic groups or 3 It is also possible to easily obtain a flocculant having multiple properties, such as a flocculant having both an anionic group and a hydrophobic bonding group or a hydrogen bonding group, and this is also one of the major features of the present invention.

There are many PN-based polymer flocculants that can be used in the present invention, some of which are shown below.

Cationic system: fNP(OCH2CH2N/Me3/Xe)2nan
fNP(OCH2CH2N・Me2)2 ntNP(O
CH2CH2NH・Me)2nan→NP(OCH2CH
2NH2) 2chintNP (NHCH2C ratio N・Me3N
e) 2nnfNP (NHCH2C ratio N・Me2) 2nn
fNP (NHCH2C ratio NH・Me) 2nnfNP (N
HCH2C ratio NH2)2chin → NP(NH2)2chin fNP(NHCH3)2nan and the above unit and another unit such as tNP
copolymer with fOR)2 or NP(OROH)2;
A copolymer or terpolymer of the above unit and another unit such as 10 NP x CI2) 2).

Anion type: fNP(OCH2000-)2nan teNP(OC6ACOO-)2chin tNP(SCH2COO-)2chin fNP(OC655S03-)2n tNP[CH(COO-)2]2chin fNP [OC3 days (COO-)2] Chin and copolymers of the above units and other units.

/Nion system: NPf○ (CH2C ratio ○na, H) 2nnfNPt○C
H2COO(CH2CH20na,H]2 chinnfNPf
NH (CH2C & 0chi IH) 2 nfNPfNHCH
2COO(CH2CQOna,H)2nan* and copolymers of the above units and other units.

Amphipathic system: fNP(NHCH2C00-)2n fNP(NHCH2C4COO-)2n→NP(N(
CH3)C ratio COO-)2nnfNP [NHCH(CO
O-)・CH2CH2COO-]2chinnfNP(NHC
6 Tsuru S03-) 2nan and a copolymer of the above unit and other units.

The PN polymer used in the present invention is a phosphonitrile dichloride polymer in which the chlorine atom or a part thereof is substituted with an anionic group, a nonionic group, a cationic group, or an amphoteric group, or is substituted with these groups. Substituted with a hydrophobic bonding group or a hydrogen bonding group.

The method for synthesizing this polymer includes ring-closing polymerization of cyclic triphosphonitrile hexachloride (PNC12)3 to produce a linear phosphonitrile dichloride polymer fPNC12nan, which is then substituted with a desired group, or Cyclic triphosphonitrile hexachloride is substituted with a desired group in advance,
There is a method in which this is then subjected to ring-opening polymerization to obtain the desired polymer.

In any case, the starting material is cyclic triphosphonitrile hexachloride, which is usually obtained by reacting phosphorus pentachloride and ammonium chloride in a solvent, followed by purification.

In addition, cyclic tetraphosphonitrile octachloride (P
NC12)4 is often used as a starting material alone or in combination with cyclic triphosphonitrile hexachloride. Note that many other synthesis methods have also been proposed.

The cyclic triphosphonitrile hexachloride is 2
When heated to a temperature of 50-350 qo, ring polymerization occurs. One example is this cyclic triphosphonitrile hexac. The lyde is placed in a Pyrex glass tube, the tube is evacuated, argon or nitrogen gas is introduced, the tube is sealed, and the tube is polymerized by heating to obtain a phosphonitrile dichloride polymer with a large molecular weight. The obtained polymer is separated and purified using a solvent such as tetrahydrofuran (THF), and the polymer obtained from the soluble portion is the desired polymer without crosslinking. The chlorine atoms in this polymer have very high reactivity. Esterization reactions, amination reactions, Friedel-Klaff reactions, etc. are easily carried out, and these reactions can be used to add compounds having an anionic group, a cationic group, or a nonionic group, or a combination of a cationic group and an anionic group to the polymer. A PN-based polymer having a desired substituent group can be obtained by reacting with a compound having this group and/or a compound having another group. When carrying out flocculation operations and filtration operations using the aforementioned PN-based polymers, conventional equipment can be used and special equipment is generally unnecessary.

The present flocculants are advantageously used in the form of dilute aqueous solutions (or suspensions in water), for example in the form of 0.1-1% aqueous solutions. It should be noted here that the present flocculant should be dissolved immediately before use, and storage in the form of an aqueous solution should be avoided. The amount of the flocculant to be used varies depending on the type of suspension, concentration, pH of the liquid, temperature and other conditions, but can be easily determined by a simple preliminary test. The description of the examples below may also serve as a guide for determining the usage amount in individual cases. This flocculant may be used together with other flocculants. Forgive me? Like the known organic polymer flocculants, N-based polymers can be advantageously used in various fields depending on their type, and they also exhibit the unique effects described above.

For example, cationic flocculants can be used for organic colloidal suspensions, flocculation of ionic organic compounds, sludge dewatering, furnace filtration acceleration, etc., such as urban sewage treatment, floor treatment, paper mill effluent treatment, pulp mill effluent treatment. The present flocculant can be advantageously used to remove sodium alkylbenzenesulfonate, promote flocculation in dye and dye factory wastewater treatment, and accelerate furnace filtration. In view of the above characteristics of the present flocculant, it goes without saying that it can be used very advantageously in activated sludge methods and the like. Anion flocculants can be used to promote the precipitation of positively charged heavy metal oxides, to flocculate proteins and other suspended substances, and for example, to separate red mud in alumina factories, to remove impurities during caustic soda production, to fish meat, Recovery of edible protein from wastewater after soaking livestock meat, treatment of raw tap water, separation of metal ions,
It can be used for collection, etc.

Nonionic flocculants can be used to flocculate relatively coarse particle suspensions, such as flocculation of powdered mineral substances, purification of blast furnace gas cleaning wastewater in steel plants, wastewater treatment of asbestos slate factories, and sedimentation of clay. Accumulation of impurities during phosphoric acid production, removal of impurities during zinc smelting, acceleration of precipitation of magnesium hydroxide during magnesia production, removal of impurities during caustic soda production, separation of oil and removal of suspended solids in petrochemical plants. It can be used for removal, wastewater treatment of pulp mills, wastewater treatment of paper mills, wastewater treatment of emulsion paint manufacturing plants, suspended matter aggregation at civil engineering construction sites, etc.

Amphoteric flocculants can be used in the same fields of use as known water-soluble protein type flocculants (eg gelatin).

A flocculant having a hydrophobic bonding group or a hydrogen bonding group in addition to a cationic active group, a nonionic active group, an anionic active group, an amphoteric active group can enhance its effectiveness and expand the field of use.

Since the agglomerated product obtained as described above generally contains a considerable amount of water, it is preferable to subject it to a dehydration operation.

Dehydration can be carried out according to a conventional method, for example, after dehydration with a centrifuge, hot air drying can be carried out. When it is in the form of a dry powder, it is convenient to store and transport, and it is also easy to apply on-site. It is also possible to mix other substances such as fertilizers, soil, organic waste (eg sawdust), pesticides, etc. before, during or after the dehydration and drying of the agglomerated product.

Field application can be carried out according to conventional methods, for example according to the same application methods as in the case of fertilizer application, customer application, etc.

Of course, it should not be used if it contains harmful heavy metals or inorganic or organic compounds. Reference Example 1 Poly[bis(methylim/)phosphazene] obtained by the reaction of polyphosphonitrile dichloride PNC12tin with methylamine is a known polymer compound, and can be represented by the following formula. .

It is somewhat unstable in water and decomposes within about 30 days. This imino compound style (molecular weight approximately 550,000
) was used to conduct the following aggregation experiment.

Finely powdered kaolin was suspended in water, left to stand overnight, the part that did not settle was collected, and the flocculant compound described above was added in the form of a 1% aqueous solution, and thoroughly mixed.

After 2 minutes, check the top lighting solution and find out the flocculant necessary to obtain a substantially transparent top lighting solution (liquid with a nephelometric turbidity of 10% or less when the turbidity is 100% without additives). The minimum required amount of

The minimum requirement in this case was 5.1 legs. On the other hand, in the case of aluminum sulfate, which is a control sample, the minimum required amount was 189 blood, and the minimum required amount of a commercially available cation type organic polymer flocculant was 13 blood. Reference Example 2 The method itself of reacting PNC12tin with alcohol to obtain a fully substituted ester is a public 3rd seal.

Using choline chloride as the monohydric alcohol, an ester body 'B} of the following formula was produced by this known reaction.The molecular weight was about 450,000.

Since it contained a quaternary ammonium group similar to this ester 'B, it could be used as a cation flocculant. The sewage containing various suspended organic and inorganic substances was allowed to stand for one hour, and the portion that did not settle was collected and placed in a sedimentation tube, and a flocculant was added thereto.

The amount of flocculant was varied and the "minimum amount of flocculant required to obtain a clear liquid after 5 minutes" was investigated. The results of this experiment were as follows. *Commercial product X: A flocculant that is a cationized modified product of polyacrylamide.

Reference example 3 Polyphosphonitrile dichloride fPNC12tin and O
The esterification reaction itself, which is a reaction with an H group-containing compound, is known.

Glycolic acid HOCH2COO as an OH group-containing compound
A sodium carboxylate group-containing compound {C} of the following formula was prepared by carrying out the above-mentioned known reaction using the sodium salt of 100%.

The molecular weight of compound [C} was 340,000. A flocculation experiment was conducted using this compound 'q as an anionic flocculant. A 5% suspension of iron oxide in water was prepared and placed in a sedimentation tube, 10 flocculants were added in the form of a 0.1% aqueous solution, and the volume of the sediment after 5 hours was measured.

The results of this experiment are shown in the table below. Reference Example 4 Cyclic phosphonitrile chloride (mixture of hexachloride and octachloride (PNC12) 3.4)
Ring-opening polymerization was carried out by heating to 50-30 mm to obtain a chain polymer (PNC12).

The above chain polymer was treated with glycol and ethylene oxide to obtain a polymer compound of the following formula.

The molecular weight of this polymer compound (1) was about 2,500,000.

A flocculation experiment was conducted using the above compound blood as a nonionic flocculant.

This compound blood was diluted with water and used as a 0.1% aqueous solution. Clarification treatment of clay wastewater (solid content 0.80%) was carried out.

The water temperature was about 20°C and the axis was about 3.0-4.0. The light transmittance of clear water was examined using a colorimetric tube with a capacity of 100 cc. The experimental results are shown in the table below. Example 1 Digested sludge from a sewage treatment plant (axis = 7.5: evaporation residue = 5.9
Various flocculants were added to suspension aggregate type 0%; suspended aggregate type material = 5.40%; various flocculants were added to suspension aggregate type ignited liquid = 62.5%), and the mixture was gently stirred and separated by sludge flocculation. Water was removed and dehydration was carried out in a press vacuum furnace.

The flocculant used in this experiment and the experimental results are shown in the table below.

It was made into a dry product with a ratio of 20%.

In addition, a cultivation test was conducted using a control sample obtained in the same manner using a cationized modified polyacrylamide (see Table 1). 20% of each was mixed into fine soil, left for 2 months, the ground was leveled, Chinese cabbage was sown, and the growth status was observed. The number of germination after 7 days of sowing reached 95% in the case of the present invention and 83% in the control, and the live weight after 30 days was 87 in the case of the present invention and 62 in the control. Ta.

Separately, celery was planted and the live weight at the time of harvest was measured, and in the case of the present invention it was 230 days, and in the control it was 185 days. Example 2 Drainage from land gravel cleaning work was allowed to stand for two hours in the field.

The supernatant containing the non-sedimented portion was treated separately with the anionic flocculant of Reference Example 3) and a known polyacrylamide-based anionic flocculant. Dehydrated cake obtained by the above flocculation operation using each flocculant flocculant {B) (see Table 1)
The amount of water used by hot air drying was IQ mosquitoes, but the flocculant flocculation rate when using the flocculant of the present invention was about three times the rate when using the control flocculant. Ta. In each case, the precipitate obtained was mixed with the precipitate obtained by the first static layer and dried.

This was used as a material. Seedling boxes were filled with each type of soil and used as cultivation beds.

After sowing the germinated rice seeds thereon, prescribed seedling-raising operations were performed, and the results were examined 25 days later. When operated according to the invention, the average plant height was 16.7, and the average weight was 2.5.
It was evening, but in contrast, in the control, the average plant height was 12.5 arcs, and the average weight was 1.7 arcs. Example 3 5% of the cationic flocculant described in Reference Example 2 was added to the sulfite pulp distillation waste liquid, based on the weight of the waste liquid, to give 50 qo.
I worshiped the rope while heating it for an hour.

The mixture was then allowed to stand still, and the resulting precipitate was separated in a furnace, centrifugally dehydrated, and dried with hot air. Separately, a directly dried product of the same waste liquid was prepared (control sample). Cultivation tests were conducted by mixing these dried substances into soil. The dried waste liquid was mixed with sandy loam at a ratio of 20%, and the soil was left in a moist state for 2 months before cultivation. After filling the Wagner pots and adding potash to each one,
Kokapu was sown and its growth status was investigated. The results of the investigation after 40 days showed that in the case of the present invention, the root weight was 65 yen, and the total weight was 14 yen.
On the other hand, in contrast, the net weight was 47 nights, and the total army was 104 days.
It was evening.

Claims (1)

[Claims] 1 General formula▲ Numerical formula, chemical formula, table, etc.▼ (Here, R^1, R^2, R^3, R^4 are cation-containing groups, anion-containing groups, hydrogen bonding groups group, halogen or inert organic group, with the proviso that R^1, R^2, R^3
, at least one of R^4 is a cation-containing group, an anion-containing group, or an aqueous-binding group) is an agglomerated product obtained by performing a solid-liquid separation operation using a polymer as a flocculant. A method for adjusting a plant medium, which comprises using the following as soil or a soil conditioner.