CN1077446C - High-activity deoxidant and preparing process thereof - Google Patents

Abstract

The present invention relates to a high-activity deoxidizing agent which is composed of active components and supporters. The present invention is characterized in that the present invention comprises 24 to 44 wt% of Mn which is used as the active components, and the supporters comprise high alumina cement, diatomite or Al2O3. The present invention is prepared by that MnCO3 and supporters are formed and then are baked at a high temperature of 300 to 450 DEG C. The present invention has the advantages of high mechanical strength, good heat resistant performance, deep deoxidizing depth and long service life; the present invention can be used at an ordinary temperature and can be heated for use, and therefore, the present invention is suitable for large-scale industrial use.

Description

A kind of high-activity deoxidant and preparation thereof

The present invention relates to the deoxy technology in the chemical industry, a kind of highly active cheap deoxidier is provided especially.

Deoxidier that pertinent literature relates to and dehydrogenation catalyst, be two big classes: the first kind is the deoxidier of chemical reaction type, as NiO, CuO etc., its deoxidation mechanism is chemical reaction-oxygen and deoxidier generation chemical reaction, reaches the deoxidation purpose; Second class is the deoxidier of catalytic reaction type, as Pd/Al ₂O ₃Deng, its deoxidation mechanism is catalytic reaction-oxygen and the hydrogen generation water that reacts, and reaches the deoxidation purpose.In China's manufacture of polyolefins, the polymerization production line of introduction generally adopts the product of import at present, produces CuO/ silica gel (UCC1101 type) as U.S.'s union carbide corporation, and domestic self-built small-entity polypropylene adopts NiO/Al ₂O ₃Type carries out deoxidation to ethene, propylene, however their shortcoming make troubles to industrial production, as: deoxidation capacity (the oxygen amount that the unit deoxidier removes) is not high, and the UCC1101 type is the 3.5ml/g deoxidier; Anti-sintering temperature is low, and the UCC1101 type is≤180 ℃; The concentration that allows to remove in advance oxygen is low, and the UCC1101 type is≤10ppm; The deoxidation degree of depth is not high, NiO/Al ₂O ₃For≤5ppm; Bad mechanical strength produces powder in transit, is difficult to quiet run in the use more; The price that also has China's copper, nickel is than manganese costliness etc., and above shortcoming has directly influenced the development of polyolefin industry.

The object of the present invention is to provide a kind of high-activity deoxidant, but its mechanical strength height, heat resistance are good, the dark normal temperature of the deoxidation degree of depth with heat down use, long service life, thereby be suitable for the large-scale industry use.

The invention provides a kind of high-activity deoxidant is made up of active component and support carrier, it is characterized in that: active component is the low oxide of manganese, the content of active component accounts for 24～44% of deoxidier gross weight by Mn, and the support carrier is alumina cement, diatomite, Al ₂O ₃Or its mixture.

The present invention also provides the preparation method of above-mentioned high-activity deoxidant, it is characterized in that:

(1) with MnCO ₃Be crushed to more than 300 orders with supporting carrier, the set of dispense ratio is MnCO by weight ₃Be 50～90%, support carrier etc. is 10～50%;

(2) with the powder compacting of (1)--process shape in blocks, bar shaped or sphere all can, size is arbitrarily;

(3) sheet of (2) moulding, bar or ball are placed to spend the night dry;

(4) place 300～400 ℃ of following roastings 2～4 hours, produce active component MnO ₂

The catalyst of method for preparing need lead to hydrogen, CO or other reducing agents before use and reduce.

The present invention also provides the preparation method of another kind of high-activity deoxidant, it is characterized in that: MnCO ₃After the carrier moulding, adopt 300～450 ℃ of high temperature, the secluding air oxygen-free atmosphere decomposes down makes deoxidier.

The present invention is to be the manganese type deoxidier that original material is produced with the abundant manganese ore of china natural resources, and it is applied in the polyolefin industry ethene, the deoxidation of the propylene degree of depth also are applicable to general conventional gas such as N ₂, H ₂, Ar, He, CO, CO ₂The even depth deoxidation.

Deoxidation mechanism of the present invention is: MnO+O ₂-Mn ₂O ₃(MnO ₂+ Mn ₃O ₄) the manganese metal oxide of divalence becomes the high price Mn oxide and reach the deoxidation purpose.Regeneration mechanism of the present invention is: Mn ₂O ₃(MnO ₂, Mn ₃O ₄)+H ₂-MnO+H ₂O high price manganese metal oxide becomes the bivalent manganese metal oxide and recovers deoxy activity.

In a word, 1. to adopt domestic resourceful manganese ore be initial feed in the present invention, produces deoxidier, and price is lower than nickel, copper, thereby be that the deoxidier that high-activity component is produced has the stronger market competitiveness with manganese.

2. the present invention has the higher deoxidation degree of depth, and at present the polymerization catalyst of polyolefin industry is brought in constant renewal in, and activity is more and more higher, thereby oxygen is removed to 5 * 10 ^-6V/v is incompatible, and O.1 requirement can reach even 0.01 * 10 ^-6V/v following (polymerization catalyst-metallocene catalyst of new generation of research, the production of propylene dimer etc. are presided over by State Scientific and Technological Commission).

3. to remove the capacity of oxygen big in the present invention, and the deoxidier life cycle of Unit Weight is long, brings convenience and energy savings and fund to operation.

4. heat resisting temperature height of the present invention, deoxidier when regenerating with hydrogen reducing, was an exothermic process after losing efficacy, and is not careful as operation, and the bed temperature of regeneration can raise suddenly, and the deoxidier that hear resistance is high is difficult for losing activity because of sintering.

5. the present invention allows the oxygen concentration height that passes through, makes its adaptive capacity extra-heavy.

6. mechanical strength of the present invention is good, phenomenons such as efflorescence loss and obstruction can not take place in the use.

7. in the alkene deoxidation process, the deoxidier of copper type and impurity acetylene reaction generate acetylene copper, thereby the danger of potential blast; The nickel type is a saturated hydrocarbons with olefin reduction easily then, brings new pollution, and manganese type and cobalt type then do not have above-mentioned side reaction.

Below by embodiment in detail the present invention is described in detail.

Example 1

Get 100 gram MnCO ₃, 100 gram alumina cements fully mix with sugar coating machine and are processed into bead, granularity 8～10 orders; The bead placement is spent the night, dry; 300～400 ℃ of following roastings 3～4 hours; After treating the nature cooling, produce and finish, standby.

Example 2

Get 100 gram MnCO ₃, 100 gram diatomite fully mix, and are processed into bar shaped, and granularity is chosen 8～10 orders, 300～400 ℃ of following roastings 3～4 hours, treats that nature cooling back is standby.

Example 3

Get 100 gram MnCO ₃, 100 gram Al ₂O ₃, both fully mix, and are processed into sphere, and granularity is chosen 8～10 orders, 300～400 ℃ of following roastings 3～4 hours, treats that nature cooling back is standby.

Example 4

MnCO by weight percentage ₃: Al ₂O ₃=80: 20, both fully mix, and are processed into 3～2mm bead, dry then, and are little right in 300～400 ℃ of following secluding air roastings 6, treat that nature cooling back is standby.

Example 5

MnCO by weight percentage ₃: alumina cement: Al ₂O ₃=70: 20: 10, after the three fully mixes, be processed into 3～2mm bead, 400 ℃ of following secluding air roastings 6 hours, treat that nature cooling back is standby.

The deoxidier of producing with example 1,2,3 is used for following deoxidation parallel laboratory test, uses H before the use ₂Reduction is handled:

Example 6 ethylene gas degree of depth deoxidations

(1) loads the bed ratio of height to diameter: L/ Φ=5

(2) oxygen content in the ethylene gas: 100 * 10 ^-6V/v

(3) gas passes through air speed: 3600/hr

(4) activating and regenerating temperature: use hydrogen reduction under 170 ℃

(5) the deoxidation degree of depth: 0.1 * 10 ^-6V/v

(6) deoxidation capacity: 5.3ml/g deoxidier

Example 7 nitrogen deoxidations

(1) loads the bed ratio of height to diameter: L/ Φ=5

(2) oxygen concentration in the nitrogen: 200 * 10 ^-6V/v

(3) gas passes through air speed: 3600/hr

(4) activating and regenerating temperature: 250 ℃

(5) deoxidation capacity: 12.4ml/g deoxidier under the normal temperature

150 ℃ of following 24ml/g deoxidiers

200 ℃ of following 27m1/g deoxidiers

(6) the deoxidation degree of depth :≤0.1 * 10 ^-6V/v

Example 8 propylene liquid phase deoxidations

(1) loads the bed ratio of height to diameter: L/ Φ=5

(2) liquid propylene oxygen content: 100ppm (mole ratio)

(3) liquid phase is passed through air speed: 7/hr

(4) activating and regenerating temperature: 350 ℃

(5) the deoxidation degree of depth :≤0.1ppm (mole ratio)

(6) deoxidation capacity: 18ml/g deoxidier

The deoxidier of producing with example 4,5 is used for following commercial Application amplification test:

Example 9

Produce 6.18 tons of deoxidiers with the method for preparing example 4; Be used for the nitrogen deoxidation that polyethylene and polypropylene are produced; Nitrogen behind the deoxidizing purification carries gas and keeps gas, blanketing gas etc. as the catalyst of polymerisation.

(1) loads the bed ratio of height to diameter: L/ Φ=5

(2) load deoxidier weight: 6.18 tons

(3) per hour pass through gas flow: 4400NM ³/ hr

(4) serviceability temperature: room temperature

(5) the deoxidation degree of depth :≤0.1 * 10 ^-6V/v

Example 10

Produce 6.5 tons of deoxidiers with the method for preparing example 4, be used for the ethene deoxidation.

(1) loads the bed ratio of height to diameter: L/ Φ=5

(2) load weight: 6.5 tons

(3) per hour pass through gas flow: 15000NM ³/ hr

(4) serviceability temperature: 70～90 ℃

(5) the deoxidation degree of depth :≤0.1 * 10 ^-6V/v

Example 11

The deoxidier of producing with preparation example 5 is used for the deoxidation of propylene liquid phase for 4.8 tons

(1) loads ratio of height to diameter: L/ Φ=5

(2) load weight: 4.8 tons

(3) per hour by the propylene amount: 6 tons/time

(4) serviceability temperature: normal temperature--40 ℃

(5) remove the oxygen degree of depth :≤0.1ppm

Comparative example

According to the document of consulting, the deoxidier that is used for olefin removal oxygen has three kinds of NiO, CuO, MnO etc., and relevant example relatively sees Table one.

The relevant example of table one relatively

The deoxidier performance	MnO/ alumina cement of the present invention, Al 2O 3	Commercially available BH-5 type NiO/Al 2O 3	American goods UCC1101 type CuO/ silica gel
				Industrial applicability	Manufacture of polyolefins ethene, the deoxidation of the propylene degree of depth	Be used for the deoxidation of propylene liquid phase	Be used for the deoxidation of the ethylene gas degree of depth
The deoxidation degree of depth	＜0.01×10 -6v/v	≤5×10 -6v/v	?＜0.1×10 -6v/v
				The deoxidation capacity	5～18ml/g	16ml/g	?3.5ml/g
Regeneration temperature	150～400 ℃ 170～300 ℃ optional	300℃	?140℃
				Heat resisting temperature (being burnt out temperature)	450℃	400℃	?200℃
Allow by the oxygen maximum concentration	5000×10 -6v/v	4000×10 -6v/v	?10×10 -6v/v
				Mechanical strength (anti-crushing power)	＞5kg/ bead can directly use	Can crush in the transportation and sieve with preceding need	Sieve with preceding need

Visible the present invention is better than the imported product UCC1101 type and the commercially available prod BH-5 type of domestic present employing at aspects such as the deoxidation degree of depth, capacity, heat resisting temperature, mechanical strengths by table, and has done the commercial Application amplification test, and achieves success.

Claims (7)

1. a sharp high-activity deoxidant is made up of active component and support carrier, and it is characterized in that: active component is the low oxide of manganese, and the content of active component accounts for 24～44% of deoxidier gross weight by Mn, and the support carrier is alumina cement, diatomite, Al ₂O ₃Or its mixture.

2. described deoxidier of claim 1 is characterized in that preparing by the following method:

(1) with MnCO ₃Be crushed to more than 300 orders with supporting carrier, the set of dispense ratio is MnCO by weight ₃Be 50～90%, supporting carrier is 10～50%;

(2), process shape in blocks, bar shaped or sphere with the powder compacting of (1);

(3) sheet of (2) moulding, bar or ball are placed to spend the night dry;

(4) place 300～400 ℃ of following roastings 2～4 hours, producing active component is MnO ₂Deoxidier.

3. by the described deoxidier of claim 2, it is characterized in that: logical hydrogen, CO or other reducing agents reduce before using.

4. described deoxidier of claim 1 is characterized in that preparing by the following method:

(1) with MnCO ₃Be crushed to more than 300 orders with supporting carrier, the set of dispense ratio is MnCO by weight ₃Be 50～90%, supporting carrier is 10～50%;

(2), process shape in blocks, bar shaped or sphere with the powder compacting of (1);

(3) sheet of (2) moulding, bar or ball are placed to spend the night dry;

(4) place under 300～450 ℃ under the secluding air oxygen-free atmosphere, to decompose and make deoxidier.

5. the preparation method of the described high-activity deoxidant of claim 1 is characterized in that may further comprise the steps:

(1) with MnCO ₃Be crushed to more than 300 orders with supporting carrier, the set of dispense ratio is MnCO by weight ₃Be 50～90%, supporting carrier is 10～50%;

(2), process shape in blocks, bar shaped or sphere with the powder compacting of (1);

(3) sheet of (2) moulding, bar or ball are placed to spend the night dry;

(4) place 300～400 ℃ of following roastings 2～4 hours, producing active component is MnO ₂Deoxidier.

6. by the described preparation method of claim 5, it is characterized in that: also comprise and use preceding logical hydrogen, CO or other reducing agents to carry out step of reducing.

7. the preparation method of the described high-activity deoxidant of claim 1 is characterized in that may further comprise the steps:

(1) with MnCO ₃Be crushed to more than 300 orders with supporting carrier, the set of dispense ratio is MnCO by weight ₃Be 50～90%, supporting carrier is 10～50%;

(2), process shape in blocks, bar shaped or sphere with the powder compacting of (1);

(3) sheet of (2) moulding, bar or ball are placed to spend the night dry;

(4) place under 300～450 ℃ under the secluding air oxygen-free atmosphere, to decompose and make deoxidier.